EP4163305B1 - Verwendung von poly-alpha-1,3-glucan-ethern als viskositätsmodifikatoren - Google Patents

Verwendung von poly-alpha-1,3-glucan-ethern als viskositätsmodifikatoren Download PDF

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Publication number
EP4163305B1
EP4163305B1 EP22190123.4A EP22190123A EP4163305B1 EP 4163305 B1 EP4163305 B1 EP 4163305B1 EP 22190123 A EP22190123 A EP 22190123A EP 4163305 B1 EP4163305 B1 EP 4163305B1
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EP
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Prior art keywords
glucan
poly alpha
viscosity
hydrocolloid
aqueous solution
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English (en)
French (fr)
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EP4163305A1 (de
Inventor
Rahul B. Kasat
Jayme L. Paullin
Andrea M. Perticone
T. Joseph Dennes
Rakesh NAMBIAR
Michael W. Cobb
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Nutrition and Biosciences USA 4 Inc
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Nutrition and Biosciences USA 4 Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/04—Polysaccharides, i.e. compounds containing more than five saccharide radicals attached to each other by glycosidic bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/48—Thickener, Thickening system
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses

Definitions

  • the invention concerns a method for increasing the viscosity of an aqueous composition.
  • This method comprises contacting a poly alpha-1,3-glucan ether compound as disclosed herein with an aqueous composition, thereby increasing the viscosity of the aqueous composition.
  • Poly alpha-1,3-glucan used to produce poly alpha-1,3-glucan ether compounds herein is preferably linear/unbranched.
  • poly alpha-1,3-glucan has no branch points or less than about 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1% branch points as a percent of the glycosidic linkages in the polymer.
  • branch points include alpha-1,6 branch points, such as those present in mutan polymer.
  • a poly alpha-1,3-glucan ether compound is termed an "ether" herein by virtue of comprising the substructure -C G -O-C-, where "-C G -" represents carbon 2, 4, or 6 of a glucose monomeric unit of a poly alpha-1,3-glucan ether compound, and where "-C-" is comprised in the organic group.
  • Poly alpha-1,3-glucan ether compounds disclosed herein are synthetic, man-made compounds.
  • an "organic group” group as used herein refers to a chain of one or more carbons that (i) has the formula -C n H 2n+1 (i.e., an alkyl group, which is completely saturated) or (ii) is mostly saturated but has one or more hydrogens substituted with another atom or functional group (i.e., a "substituted alkyl group”). Such substitution may be with one or more hydroxyl groups, oxygen atoms (thereby forming an aldehyde or ketone group), carboxyl groups, or other alkyl groups.
  • a "halide” herein refers to a compound comprising one or more halogen atoms (e.g., fluorine, chlorine, bromine, iodine).
  • a halide herein can refer to a compound comprising one or more halide groups such as fluoride, chloride, bromide, or iodide.
  • a halide group may serve as a reactive group of an etherification agent.
  • reaction refers to a reaction comprising at least poly alpha-1,3-glucan and an etherification agent. These components are typically dissolved and/or mixed in an aqueous alkali hydroxide. A reaction is placed under suitable conditions (e.g., time, temperature) for the etherification agent to etherify one or more hydroxyl groups of the glucose units of poly alpha-1,3-glucan with an organic group, thereby yielding a poly alpha-1,3-glucan ether compound.
  • suitable conditions e.g., time, temperature
  • poly alpha-1,3-glucan slurry refers to an aqueous mixture comprising the components of a glucosyltransferase enzymatic reaction such as poly alpha-1,3-glucan, sucrose, one or more glucosyltransferase enzymes, glucose and fructose.
  • a glucosyltransferase enzymatic reaction such as poly alpha-1,3-glucan, sucrose, one or more glucosyltransferase enzymes, glucose and fructose.
  • This composition is a slurry since the poly alpha-1,3-glucan is not dissolved therein.
  • poly alpha-1,3-glucan wet cake herein refers to poly alpha-1,3-glucan that has been separated from a slurry and washed with water or an aqueous solution. Poly alpha-1,3-glucan is not completely dried when preparing a wet cake.
  • degree of substitution refers to the average number of hydroxyl groups substituted in each monomeric unit (glucose) of a poly alpha-1,3-glucan ether compound. Since there are three hydroxyl groups in each monomeric unit in poly alpha-1,3-glucan, the degree of substitution in a poly alpha-1,3-glucan ether compound herein can be no higher than 3.
  • crosslink refers to a chemical bond, atom, or group of atoms that connects two adjacent atoms in one or more polymer molecules. It should be understood that, in a composition comprising crosslinked poly alpha-1,3-glucan ether, crosslinks can be between at least two poly alpha-1,3-glucan ether molecules (i.e., intermolecular crosslinks); there can also be intramolecular crosslinking.
  • a "crosslinking agent” as used herein is an atom or compound that can create crosslinks.
  • aqueous composition refers to a solution or mixture in which the solvent is at least about 20 wt% water, for example, and which comprises poly alpha-1,3-glucan and/or a poly alpha-1,3-glucan ether compound.
  • aqueous compositions herein are aqueous solutions and hydrocolloids.
  • a 'dispersion refers to an aqueous composition comprising one or more particles (e.g., any ingredient of a personal care product, pharmaceutical product, food product, household product, or industrial product disclosed herein) that are scattered, or uniformly scattered, throughout the aqueous composition. It is believed that poly alpha-1,3-glucan and/or poly alpha-1,3-glucan ether compounds can act as dispersants in aqueous compositions disclosed herein.
  • contacting refers to any action that results in bringing together an aqueous composition with poly alpha-1,3-glucan and/or a poly alpha-1,3-glucan ether compound. Contacting can be performed by any means known in the art, such as dissolving, mixing, shaking, or homogenization, for example.
  • fabric refers to a woven material having a network of natural and/or artificial fibers.
  • Such fibers can be thread or yarn, for example.
  • a “fabric care composition” herein is any composition suitable for treating fabric in some manner.
  • Examples of such a composition include laundry detergents and fabric softeners.
  • heavy duty detergent and “all-purpose detergent” are used interchangeably herein to refer to a detergent useful for regular washing of white and colored textiles at any temperature.
  • low duty detergent or “fine fabric detergent” are used interchangeably herein to refer to a detergent useful for the care of delicate fabrics such as viscose, wool, silk, microfiber or other fabric requiring special care.
  • Special care can include conditions of using excess water, low agitation, and/or no bleach, for example.
  • oral care composition herein is any composition suitable for treating an soft or hard surface in the oral cavity such as dental (teeth) and/or gum surfaces.
  • adsorption herein refers to the adhesion of a compound (e.g., poly alpha-1,3-glucan ether) to the surface of a material.
  • the "molecular weight" of poly alpha-1,3-glucan and poly alpha-1,3-glucan ether compounds herein can be represented as number-average molecular weight (M n ) or as weight-average molecular weight (M w ).
  • M n number-average molecular weight
  • M w weight-average molecular weight
  • molecular weight can be represented as Daltons, grams/mole, DPw (weight average degree of polymerization), or DPn (number average degree of polymerization).
  • DPw weight average degree of polymerization
  • DPn number average degree of polymerization
  • percent by volume percent by volume
  • volume percent percent by volume
  • vol % percent by volume
  • v/v % percent by volume
  • Embodiments of the disclosed invention concern a hydrocolloid or aqueous solution comprising a poly alpha-1,3-glucan ether compound represented by the structure:
  • the DoS of a poly alpha-1,3-glucan ether compound disclosed herein can affect the viscosity of the hydrocolloid or aqueous solution comprising the compound.
  • a hydrocolloid or aqueous solution comprising carboxymethyl poly alpha-1,3-glucan (CMG) with a DoS of about 0.4-0.6 has greater viscosity than a hydrocolloid or aqueous solution comprising CMG with higher DoS (e.g., about 0.8-1.0).
  • n can have a value of at least 25, 50, 75, 100, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, or 4000 (or any integer between 25 and 4000), for example.
  • n in still other examples can be in a range of 25-250, 50-250, 75-250, 100-250, 150-250, 200-250, 25-200, 50-200, 75-200, 100-200, 150-200, 25-150, 50-150, 75-150, 100-150, 25-100, 50-100, 75-100, 25-75, 50-75, or 25-50.
  • dihydroxy alkyl groups such as dihydroxymethyl, dihydroxyethyl (e.g., -CH(OH)CH 2 OH), dihydroxypropyl (e.g., -CH 2 CH(OH)CH 2 OH, -CH(OH)CH(OH)CH 3 ), dihydroxybutyl and dihydroxypentyl groups.
  • one or more carbons of an alkyl group can have a substitution(s) with another alkyl group.
  • substituent alkyl groups are methyl, ethyl and propyl groups.
  • an R group can be -CH(CH 3 )CH 2 CH 3 or -CH 2 CH(CH 3 )CH 3 , for example, which are both propyl groups having a methyl substitution.
  • a substitution (e.g., hydroxy or carboxy group) on an alkyl group in certain embodiments may be bonded to the terminal carbon atom of the alkyl group, where the terminal carbon group is opposite the terminus that is in ether linkage to the glucose group in the glucan ether compound (above formula).
  • An example of this terminal substitution is in the hydroxypropyl group -CH 2 CH 2 CH 2 OH.
  • a substitution may be on an internal carbon atom of an alkyl group.
  • An example on an internal substitution is in the hydroxypropyl group -CH 2 CH(OH)CH 3 .
  • An alkyl group can have one or more substitutions, which may be the same (e.g., two hydroxyl groups [dihydroxy]) or different (e.g., a hydroxyl group and a carboxyl group).
  • Hydrocolloids or aqueous solutions comprising a poly alpha-1,3-glucan ether compound disclosed herein have a viscosity of at least about 10 cPs.
  • a hydrocolloid or aqueous solution herein has a viscosity of at least about 100, 250, 500, 750, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10000, 10500, 11000, 12000, 13000, 14000, 15000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, or 100000 cPs (or any integer between 100 and 100000 cPs), for example.
  • Viscosity can be measured with the hydrocolloid or aqueous solution at any temperature between about 3 °C to about 110 °C (or any integer between 3 and 110 °C), for example. Alternatively, viscosity can be measured at a temperature between about 4 °C to 30 °C, or about 20 °C to 25 °C. Viscosity can be measured at atmospheric pressure (about 760 torr) or any other higher or lower pressure.
  • the viscosity of a hydrocolloid or aqueous solution disclosed herein can be measured using a viscometer or rheometer, or using any other means known in the art. It would be understood by those skilled in the art that a rheometer can be used to measure the viscosity of those hydrocolloids and aqueous solutions of the invention that exhibit shear thinning behavior or shear thickening behavior (i.e., liquids with viscosities that vary with flow conditions).
  • the viscosity of such embodiments can be measured at a rotational shear rate of about 10 to 1000 rpm (revolutions per minute) (or any integer between 10 and 1000 rpm), for example.
  • viscosity can be measured at a rotational shear rate of about 10, 60, 150, 250, or 600 rpm.
  • a poly alpha-1,3-glucan ether compound can be in an anionic form in a hydrocolloid or aqueous solution.
  • examples may include those poly alpha-1,3-glucan ether compounds having an organic group comprising an alkyl group substituted with a carboxyl group.
  • Carboxyl (COOH) groups in a carboxyalkyl poly alpha-1,3-glucan ether compound can convert to carboxylate (COO - ) groups in aqueous conditions.
  • Such anionic groups can interact with salt cations such as any of those listed above in (i) (e.g., potassium, sodium, or lithium cation).
  • a poly alpha-1,3-glucan ether compound can be a sodium carboxyalkyl poly alpha-1,3-glucan ether (e.g., sodium carboxymethyl poly alpha-1,3-glucan), potassium carboxyalkyl poly alpha-1,3-glucan ether (e.g., potassium carboxymethyl poly alpha-1,3-glucan), or lithium carboxyalkyl poly alpha-1,3-glucan ether (e.g., lithium carboxymethyl poly alpha-1,3-glucan), for example.
  • sodium carboxyalkyl poly alpha-1,3-glucan ether e.g., sodium carboxymethyl poly alpha-1,3-glucan
  • potassium carboxyalkyl poly alpha-1,3-glucan ether e.g., potassium carboxymethyl poly alpha-1,3-glucan
  • lithium carboxyalkyl poly alpha-1,3-glucan ether e.g., lithium carboxymethyl poly alpha-1,3-glucan
  • a composition comprising poly alpha-1,3-glucan and/or a poly alpha-1,3-glucan ether compound herein can be non-aqueous (e.g., a dry composition).
  • non-aqueous or dry composition typically has less than 3, 2, 1, 0.5, or 0.1 wt% water comprised therein.
  • a poly alpha-1,3-glucan ether compound comprised in certain embodiments of the disclosed composition may be crosslinked using any means known in the art.
  • Such crosslinks may be borate crosslinks, where the borate is from any boron-containing compound (e.g., boric acid, diborates, tetraborates, pentaborates, polymeric compounds such as Polybor ® , polymeric compounds of boric acid, alkali borates), for example.
  • crosslinks can be provided with polyvalent metals such as titanium or zirconium. Titanium crosslinks may be provided, for example, using titanium IV-containing compounds such as titanium ammonium lactate, titanium triethanolamine, titanium acetylacetonate, and polyhydroxy complexes of titanium.
  • Zirconium crosslinks can be provided using zirconium IV-containing compounds such as zirconium lactate, zirconium carbonate, zirconium acetylacetonate, zirconium triethanolamine, zirconium diisopropylamine lactate and polyhydroxy complexes of zirconium, for example.
  • crosslinks can be provided with any crosslinking agent described in U.S. Patent Nos. 4462917 , 4464270 , 4477360 and 4799550 .
  • a crosslinking agent e.g., borate
  • a crosslinking agent may be present in an aqueous composition herein at a concentration of about 0.2% to 20 wt%, or about 0.1, 0.2, 0.3, 0.4, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, or 20 wt%, for example.
  • a composition herein may optionally contain one or more active enzymes.
  • suitable enzymes include proteases, cellulases, hemicellulases, peroxidases, lipolytic enzymes (e.g., metallolipolytic enzymes), xylanases, lipases, phospholipases, esterases (e.g., arylesterase, polyesterase), perhydrolases, cutinases, pectinases, pectate lyases, mannanases, keratinases, reductases, oxidases (e.g., choline oxidase), phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, beta-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases, metalloproteinases, amadoria
  • a cellulase herein may be derived from any microbial source, such as a bacteria or fungus. Chemically-modified cellulases or protein-engineered mutant cellulases are included. Suitable cellulases include, but are not limited to, cellulases from the genera Bacillus , Pseudomonas , Streptomyces , Trichoderma , Humicola , Fusarium , Thielavia and Acremonium. As other examples, a cellulase may be derived from Humicola insolens , Myceliophthora thermophila or Fusarium oxysporum ; these and other cellulases are disclosed in U.S. Patent Nos.
  • Exemplary Trichoderma reesei cellulases are disclosed in U.S. Patent Nos. 4689297 , 5814501 , 5324649 , and International Patent Appl. Publ. Nos. WO92/06221 and WO92/06165 .
  • Exemplary Bacillus cellulases are disclosed in U.S. Patent No. 6562612 .
  • a cellulase, such as any of the foregoing, preferably is in a mature form lacking an N-terminal signal peptide.
  • One or more cellulases can be directly added as an ingredient when preparing the disclosed composition.
  • one or more cellulases can be indirectly (inadvertently) provided in the disclosed composition.
  • cellulase can be provided in a composition herein by virtue of being present in a non-cellulase enzyme preparation used for preparing the composition.
  • Cellulase in compositions in which cellulase is indirectly provided thereto can be present at about 0.1-10 ppb (e.g., less than 1 ppm), for example.
  • a benefit of a composition herein by virtue of employing a poly alpha-1,3-glucan ether compound instead of a cellulose ether compound, is that non-cellulase enzyme preparations that might have background cellulase activity can be used without concern that the desired effects of the glucan ether will be negated by the background cellulase activity.
  • a cellulase in certain embodiments can be thermostable.
  • Cellulase thermostability refers to the ability of the enzyme to retain activity after exposure to an elevated temperature (e.g. about 60-70 °C) for a period of time (e.g., about 30-60 minutes).
  • the thermostability of a cellulase can be measured by its half-life (t1/2) given in minutes, hours, or days, during which time period half the cellulase activity is lost under defined conditions.
  • a cellulase in certain embodiments can be stable to a wide range of pH values (e.g. neutral or alkaline pH such as pH of ⁇ 7.0 to ⁇ 11.0). Such enzymes can remain stable for a predetermined period of time (e.g., at least about 15 min., 30 min., or 1 hour) under such pH conditions.
  • pH values e.g. neutral or alkaline pH such as pH of ⁇ 7.0 to ⁇ 11.0.
  • Such enzymes can remain stable for a predetermined period of time (e.g., at least about 15 min., 30 min., or 1 hour) under such pH conditions.
  • At least one, two, or more cellulases may be included in the composition, for example.
  • the total amount of cellulase in a composition herein typically is an amount that is suitable for the purpose of using cellulase in the composition (an "effective amount").
  • an effective amount of cellulase in a composition intended for improving the feel and/or appearance of a cellulose-containing fabric is an amount that produces measurable improvements in the feel of the fabric (e.g., improving fabric smoothness and/or appearance, removing pills and fibrils which tend to reduce fabric appearance sharpness).
  • an effective amount of cellulase in a fabric stonewashing composition herein is that amount which will provide the desired effect (e.g., to produce a worn and faded look in seams and on fabric panels).
  • the amount of cellulase in a composition herein can also depend on the process parameters in which the composition is employed (e.g., equipment, temperature, time, and the like) and cellulase activity, for example.
  • the effective concentration of cellulase in an aqueous composition in which a fabric is treated can be readily determined by a skilled artisan.
  • Personal care products herein are not particularly limited and include, for example, skin care compositions, cosmetic compositions, antifungal compositions, and antibacterial compositions.
  • Personal care products herein may be in the form of, for example, lotions, creams, pastes, balms, ointments, pomades, gels, liquids, combinations of these and the like.
  • the personal care products disclosed herein can include at least one active ingredient, if desired.
  • An active ingredient is generally recognized as an ingredient that causes an intended pharmacological effect.
  • a detergent composition herein may be in any useful form, e.g., as powders, granules, pastes, bars, unit dose, or liquid.
  • a liquid detergent may be aqueous, typically containing up to about 70 wt% of water and 0 wt% to about 30 wt% of organic solvent. It may also be in the form of a compact gel type containing only about 30 wt% water.
  • Builders include, but are not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphates, alkali metal silicates, alkaline earth and alkali metal carbonates, aluminosilicates, polycarboxylate compounds, ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, citric acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • a detergent composition herein can comprise at least one chelating agent.
  • Suitable chelating agents include, but are not limited to copper, iron and/or manganese chelating agents and mixtures thereof.
  • the composition comprises from about 0.1% to about 15%, or even from about 3.0% to about 10%, chelating agent by weight of the composition.
  • Suitable proteases include those of animal, vegetable or microbial origin. In some embodiments, microbial proteases are used. In some embodiments, chemically or genetically modified mutants are included.
  • the protease is a serine protease, preferably an alkaline microbial protease or a trypsin-like protease.
  • alkaline proteases include subtilisins, especially those derived from Bacillus (e.g., subtilisin, lentus, amyloliquefaciens, subtilisin Carlsberg, subtilisin 309, subtilisin 147 and subtilisin 168). Additional examples include those mutant proteases described in U.S. Pat. Nos.
  • cloned lipases find use in some embodiments of the present invention, including but not limited to, Penicillium camembertii lipase (See, Yamaguchi et al., Gene 103:61-67 [1991 ]), Geotricum candidum lipase (See, Schimada et al., J. Biochem., 106:383-388 [1989 ]), and various Rhizopus lipases such as R. delemar lipase (See, Hass et al., Gene 109:117-113 [1991 ]), a R. niveus lipase ( Kugimiya et al., Biosci. Biotech. Biochem.
  • Additional lipases useful herein include, for example, those disclosed in WO92/05249 , WO94/01541 , WO95/35381 , WO96/00292 , WO95/30744 , WO94/25578 , WO95/14783 , WO95/22615 , WO97/04079 , WO97/07202 , EP407225 and EP260105 .
  • Suitable polyesterases include, for example, those disclosed in WO01/34899 , WO01/14629 and U.S. Patent No. 6933140 .
  • a detergent composition herein can also comprise 2,6-beta-D-fructan hydrolase, which is effective for removal/cleaning of certain biofilms present on household and/or industrial textiles/laundry.
  • Additional suitable amylases include those disclosed in WO9510603 , WO9526397 , WO9623874 , WO9623873 , WO9741213 , WO9919467 , WO0060060 , WO0029560 , WO9923211 , WO9946399 , WO0060058 , WO0060059 , WO9942567 , WO0114532 , WO02092797 , WO0166712 , WO0188107 , WO0196537 , WO0210355 , WO9402597 , WO0231124 , WO9943793 , WO9943794 , WO2004113551 , WO2005001064 , WO2005003311 , WO0164852 , WO2006063594 , WO2006066594 , WO2006066596 , WO2006012899 , WO20080929
  • Suitable amylases include, for example, commercially available amylases such as STAINZYME ® , STAINZYME PLUS ® , NATALASE ® , DURAMYL ® , TERMAMYL ® , TERMAMYL ULTRA ® , FUNGAMYL ® and BAN TM (Novo Nordisk A/S and Novozymes A/S); RAPIDASE ® , POWERASE ® , PURASTAR ® and PREFERENZ TM (DuPont Industrial Biosciences).
  • Suitable peroxidases/oxidases contemplated for use in the compositions include those of plant, bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of peroxidases useful herein include those from the genus Coprinus (e.g., C. cinereus , WO93/24618 , WO95/10602 , and WO98/15257 ), as well as those referenced in WO2005056782 , WO2007106293 , WO2008063400 , WO2008106214 , and WO2008106215 . Commercially available peroxidases useful herein include, for example, GUARDZYME TM (Novo Nordisk A/S and Novozymes A/S).
  • peroxidases are used in combination with hydrogen peroxide or a source thereof (e.g., a percarbonate, perborate or persulfate) in the compositions of the present invention.
  • oxidases are used in combination with oxygen. Both types of enzymes are used for "solution bleaching" (i.e., to prevent transfer of a textile dye from a dyed fabric to another fabric when the fabrics are washed together in a wash liquor), preferably together with an enhancing agent (See e.g., WO94/12621 and WO95/01426 ).
  • Suitable peroxidases/oxidases include, but are not limited to, those of plant, bacterial or fungal origin. Chemically or genetically modified mutants are included in some embodiments.
  • Enzymes that may be comprised in a detergent composition herein may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol; a sugar or sugar alcohol; lactic acid; boric acid or a boric acid derivative (e.g., an aromatic borate ester).
  • a polyol such as propylene glycol or glycerol
  • a sugar or sugar alcohol lactic acid
  • boric acid or a boric acid derivative e.g., an aromatic borate ester
  • a detergent composition herein may contain about 1 wt% to about 65 wt% of a detergent builder or complexing agent such as zeolite, diphosphate, triphosphate, phosphonate, citrate, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTMPA), alkyl- or alkenylsuccinic acid, soluble silicates or layered silicates (e.g., SKS-6 from Hoechst).
  • a detergent may also be unbuilt, i.e., essentially free of detergent builder.
  • a detergent composition in certain embodiments may comprise one or more other types of polymers in addition to a poly alpha-1,3-glucan and/or poly alpha-1,3-glucan ether compound.
  • examples of other types of polymers useful herein include carboxymethyl cellulose (CMC), poly(vinylpyrrolidone) (PVP), polyethylene glycol (PEG), poly(vinyl alcohol) (PVA), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
  • a detergent composition herein may contain a bleaching system.
  • a bleaching system can comprise an H 2 O 2 source such as perborate or percarbonate, which may be combined with a peracid-forming bleach activator such as tetraacetylethylenediamine (TAED) or nonanoyloxybenzenesulfonate (NOBS).
  • TAED tetraacetylethylenediamine
  • NOBS nonanoyloxybenzenesulfonate
  • TAED tetraacetylethylenediamine
  • NOBS nonanoyloxybenzenesulfonate
  • a bleaching system may comprise peroxyacids (e.g., amide, imide, or sulfone type peroxyacids).
  • a bleaching system can be an enzymatic bleaching system comprising perhydrolase, for example, such as the system described in WO2005/056783 .
  • a detergent composition herein may also contain conventional detergent ingredients such as fabric conditioners, clays, foam boosters, suds suppressors, anti-corrosion agents, soil-suspending agents, anti-soil redeposition agents, dyes, bactericides, tarnish inhibitors, optical brighteners, or perfumes.
  • the pH of a detergent composition herein is usually neutral or alkaline (e.g., pH of about 7.0 to about 11.0).
  • detergent compositions that can be adapted for purposes disclosed herein are disclosed in, for example, US20090209445A1 , US20100081598A1 , US7001878B2 , EP1504994B1 , WO2001085888A2 , WO2003089562A1 , WO2009098659A1 , WO2009098660A1 , WO2009112992A1 , WO2009124160A1 , WO2009152031A1 , WO2010059483A1 , WO2010088112A1 , WO2010090915A1 , WO2010135238A1 , WO2011094687A1 , WO2011094690A1 , WO2011127102A1 , WO2011163428A1 , WO2008000567A1 , WO2006045391A1 , WO2006007911A1 , WO2012027404A1 , EP1740690B1 , WO
  • Laundry detergent compositions herein can optionally be heavy duty (all purpose) laundry detergent compositions.
  • exemplary heavy duty laundry detergent compositions comprise a detersive surfactant (10%-40% wt/wt), including an anionic detersive surfactant (selected from a group of linear or branched or random chain, substituted or unsubstituted alkyl sulphates, alkyl sulphonates, alkyl alkoxylated sulphate, alkyl phosphates, alkyl phosphonates, alkyl carboxylates, and/or mixtures thereof), and optionally non-ionic surfactant (selected from a group of linear or branched or random chain, substituted or unsubstituted alkyl alkoxylated alcohol, e.g., C8-C18 alkyl ethoxylated alcohols and/or C6-C12 alkyl phenol alkoxylates), where the weight ratio of anionic detersive surfactant (with a
  • Suitable detersive surfactants also include cationic detersive surfactants (selected from a group of alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl ternary sulphonium compounds, and/or mixtures thereof); zwitterionic and/or amphoteric detersive surfactants (selected from a group of alkanolamine sulpho-betaines); ampholytic surfactants; semi-polar non-ionic surfactants and mixtures thereof.
  • cationic detersive surfactants selected from a group of alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl ternary sulphonium compounds, and/or mixtures thereof
  • zwitterionic and/or amphoteric detersive surfactants selected from a group of alkanolamine sulpho-betaines
  • a detergent herein such as a heavy duty laundry detergent composition may optionally include additional polymers such as soil release polymers (include anionically end-capped polyesters, for example SRP1, polymers comprising at least one monomer unit selected from saccharide, dicarboxylic acid, polyol and combinations thereof, in random or block configuration, ethylene terephthalate-based polymers and co-polymers thereof in random or block configuration, for example REPEL-O-TEX SF, SF-2 AND SRP6, TEXCARE SRA100, SRA300, SRN100, SRN170, SRN240, SRN300 AND SRN325, MARLOQUEST SL), antiredeposition polymers (0.1 wt% to 10 wt%), include carboxylate polymers, such as polymers comprising at least one monomer selected from acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid,
  • a detergent herein such as a heavy duty laundry detergent composition may optionally further include dye transfer inhibiting agents, examples of which include manganese phthalocyanine, peroxidases, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles and/or mixtures thereof; chelating agents, examples of which include ethylene-diamine-tetraacetic acid (EDTA), diethylene triamine penta methylene phosphonic acid (DTPMP), hydroxy-ethane diphosphonic acid (HEDP), ethylenediamine N,N'-disuccinic acid (EDDS), methyl glycine diacetic acid (MGDA), diethylene triamine penta acetic acid (DTPA), propylene diamine tetracetic acid (PDTA), 2-hydroxypyridine-N-oxide (HPNO), or methyl g
  • a detergent herein such as a heavy duty laundry detergent composition may optionally include silicone or fatty-acid based suds suppressors; hueing dyes, calcium and magnesium cations, visual signaling ingredients, anti-foam (0.001 wt% to about 4.0 wt%), and/or a structurant/thickener (0.01 wt% to 5 wt%) selected from the group consisting of diglycerides and triglycerides, ethylene glycol distearate, microcrystalline cellulose, microfiber cellulose, biopolymers, xanthan gum, gellan gum, and mixtures thereof).
  • Such structurant/thickener would be in addition to the one or more poly alpha-1,3-glucan compounds comprised in the detergent.
  • a detergent herein can be in the form of a heavy duty dry/solid laundry detergent composition, for example.
  • a detergent may include: (i) a detersive surfactant, such as any anionic detersive surfactant disclosed herein, any non-ionic detersive surfactant disclosed herein, any cationic detersive surfactant disclosed herein, any zwitterionic and/or amphoteric detersive surfactant disclosed herein, any ampholytic surfactant, any semi-polar non-ionic surfactant, and mixtures thereof; (ii) a builder, such as any phosphate-free builder (e.g., zeolite builders in the range of 0 wt% to less than 10 wt%), any phosphate builder (e.g., sodium tri-polyphosphate in the range of 0 wt% to less than 10 wt%), citric acid, citrate salts and nitrilotriacetic acid, any silicate salt (e.g., sodium
  • compositions disclosed herein can be in the form of a dishwashing detergent composition.
  • dishwashing detergents include automatic dishwashing detergents (typically used in dishwasher machines) and hand-washing dish detergents.
  • a dishwashing detergent composition can be in any dry or liquid/aqueous form as disclosed herein, for example.
  • Components that may be included in certain embodiments of a dishwashing detergent composition include, for example, one or more of a phosphate; oxygen- or chlorine-based bleaching agent; non-ionic surfactant; alkaline salt (e.g., metasilicates, alkali metal hydroxides, sodium carbonate); any active enzyme disclosed herein; anti-corrosion agent (e.g., sodium silicate); anti-foaming agent; additives to slow down the removal of glaze and patterns from ceramics; perfume; anti-caking agent (in granular detergent); starch (in tablet-based detergents); gelling agent (in liquid/gel based detergents); and/or sand (powdered detergents).
  • alkaline salt e.g., metasilicates, alkali metal hydroxides, sodium carbonate
  • anti-corrosion agent e.g., sodium silicate
  • anti-foaming agent additives to slow down the removal of glaze and patterns from ceramics
  • perfume anti-caking agent (in
  • Dishwashing detergents such as an automatic dishwasher detergent or liquid dishwashing detergent can comprise (i) a non-ionic surfactant, including any ethoxylated non-ionic surfactant, alcohol alkoxylated surfactant, epoxy-capped poly(oxyalkylated) alcohol, or amine oxide surfactant present in an amount from 0 to 10 wt%; (ii) a builder, in the range of about 5-60 wt%, including any phosphate builder (e.g., mono-phosphates, di-phosphates, tri-polyphosphates, other oligomeric-polyphosphates, sodium tripolyphosphate-STPP), any phosphate-free builder (e.g., amino acid-based compounds including methyl-glycine-diacetic acid [MGDA] and salts or derivatives thereof, glutamic-N,N-diacetic acid [GLDA] and salts or derivatives thereof, iminodisuccinic acid (IDS) and salts
  • detergent formulations comprising at least one poly alpha-1,3-glucan ether compound (e.g., a carboxyalkyl poly alpha-1,3-glucan ether such as carboxymethyl poly alpha-1,3-glucan [CMG]) are disclosed below (1-19):
  • a poly alpha-1,3-glucan ether compound e.g., a carboxyalkyl poly alpha-1,3-glucan ether such as carboxymethyl poly alpha-1,3-glucan [CMG]
  • detergent formulations can be adapted to include a poly alpha-1,3-glucan ether compound.
  • examples include PUREX ® ULTRAPACKS (Henkel), FINISH ® QUANTUM (Reckitt Benckiser), CLOROX TM 2 PACKS (Clorox), OXICLEAN MAX FORCE POWER PAKS (Church & Dwight), TIDE ® STAIN RELEASE, CASCADE ® ACTIONPACS, and TIDE ® PODS TM (Procter & Gamble).
  • compositions disclosed herein can be in the form of an oral care composition.
  • oral care compositions include dentifrices, toothpaste, mouth wash, mouth rinse, chewing gum, and edible strips that provide some form of oral care (e.g., treatment or prevention of cavities [dental caries], gingivitis, plaque, tartar, and/or periodontal disease).
  • An oral care composition can also be for treating an "oral surface", which encompasses any soft or hard surface within the oral cavity including surfaces of the tongue, hard and soft palate, buccal mucosa, gums and dental surfaces.
  • a "dental surface” herein is a surface of a natural tooth or a hard surface of artificial dentition including a crown, cap, filling, bridge, denture, or dental implant, for example.
  • One or more poly alpha-1,3-glucan and/or poly alpha-1,3-glucan ether compounds comprised in an oral care composition typically are provided therein as a thickening agent and/or dispersion agent, which may be useful to impart a desired consistency and/or mouth feel to the composition.
  • An oral care composition herein can comprise about 0.01-15.0 wt% (e.g., -0.1-10 wt% or -0.1-5.0 wt%, -0.1-2.0 wt%) of one or more poly alpha-1,3-glucan and/or poly alpha-1,3-glucan ether compounds disclosed herein (e.g., a carboxyalkyl poly alpha-1,3-glucan ether such as carboxymethyl poly alpha-1,3-glucan [CMG]), for example.
  • poly alpha-1,3-glucan and/or poly alpha-1,3-glucan ether compounds disclosed herein e.g., a carboxyalkyl poly alpha-1,3-glucan ether such as carboxymethyl poly alpha-1,3-glucan [CMG]
  • One or more other thickening agents or dispersion agents can also be provided in an oral care composition herein, such as a carboxyvinyl polymer, carrageenan (e.g., L-carrageenan), natural gum (e.g., karaya, xanthan, gum arabic, tragacanth), colloidal magnesium aluminum silicate, or colloidal silica, for example.
  • carrageenan e.g., L-carrageenan
  • natural gum e.g., karaya, xanthan, gum arabic, tragacanth
  • colloidal magnesium aluminum silicate e.g., colloidal magnesium aluminum silicate, or colloidal silica, for example.
  • An oral care composition herein may be a toothpaste or other dentifrice, for example.
  • Such compositions, as well as any other oral care composition herein can additionally comprise, without limitation, one or more of an anticaries agent, antimicrobial or antibacterial agent, anticalculus or tartar control agent, surfactant, abrasive, pH-modifying agent, foam modulator, humectant, flavorant, sweetener, pigment/colorant, whitening agent, and/or other suitable components.
  • Examples of oral care compositions to which one or more poly alpha-1,3-glucan ether compounds can be added are disclosed in U.S. Patent Appl. Publ. Nos. 2006/0134025 , 2002/0022006 and 2008/0057007 .
  • An anticaries agent herein can be an orally acceptable source of fluoride ions.
  • Suitable sources of fluoride ions include fluoride, monofluorophosphate and fluorosilicate salts as well as amine fluorides, including olaflur (N'-octadecyltrimethylendiamine-N,N,N'- tris(2-ethanol)-dihydrofluoride), for example.
  • An anticaries agent can be present in an amount providing a total of about 100-20000 ppm, about 200-5000 ppm, or about 500-2500 ppm, fluoride ions to the composition, for example.
  • sodium fluoride is the sole source of fluoride ions
  • an amount of about 0.01-5.0 wt%, about 0.05-1.0 wt%, or about 0.1-0.5 wt%, sodium fluoride can be present in the composition, for example.
  • An antimicrobial or antibacterial agent suitable for use in an oral care composition herein includes, for example, phenolic compounds (e.g., 4-allylcatechol; p-hydroxybenzoic acid esters such as benzylparaben, butylparaben, ethylparaben, methylparaben and propylparaben; 2-benzylphenol; butylated hydroxyanisole; butylated hydroxytoluene; capsaicin; carvacrol; creosol; eugenol; guaiacol; halogenated bisphenolics such as hexachlorophene and bromochlorophene; 4-hexylresorcinol; 8-hydroxyquinoline and salts thereof; salicylic acid esters such as menthyl salicylate, methyl salicylate and phenyl salicylate; phenol; pyrocatechol; salicylanilide; thymol; halogenated diphenylether compounds such as tric
  • One or more antimicrobial agents can optionally be present at about 0.01-10 wt% (e
  • Useful inorganic phosphate and polyphosphate salts include, for example, monobasic, dibasic and tribasic sodium phosphates, sodium tripolyphosphate, tetrapolyphosphate, mono-, di-, tri- and tetra-sodium pyrophosphates, disodium dihydrogen pyrophosphate, sodium trimetaphosphate, sodium hexametaphosphate, or any of these in which sodium is replaced by potassium or ammonium.
  • Other useful anticalculus agents in certain embodiments include anionic polycarboxylate polymers (e.g., polymers or copolymers of acrylic acid, methacrylic, and maleic anhydride such as polyvinyl methyl ether/maleic anhydride copolymers).
  • Still other useful anticalculus agents include sequestering agents such as hydroxycarboxylic acids (e.g., citric, fumaric, malic, glutaric and oxalic acids and salts thereof) and aminopolycarboxylic acids (e.g., EDTA).
  • hydroxycarboxylic acids e.g., citric, fumaric, malic, glutaric and oxalic acids and salts thereof
  • aminopolycarboxylic acids e.g., EDTA
  • One or more anticalculus or tartar control agents can optionally be present at about 0.01-50 wt% (e.g., about 0.05-25 wt% or about 0.1-15 wt%), for example, in the disclosed oral care composition.
  • a surfactant suitable for use in an oral care composition herein may be anionic, non-ionic, or amphoteric, for example.
  • Suitable anionic surfactants include, without limitation, water-soluble salts of C 8-20 alkyl sulfates, sulfonated monoglycerides of C 8-20 fatty acids, sarcosinates, and taurates.
  • anionic surfactants include sodium lauryl sulfate, sodium coconut monoglyceride sulfonate, sodium lauryl sarcosinate, sodium lauryl isoethionate, sodium laureth carboxylate and sodium dodecyl benzenesulfonate.
  • Suitable non-ionic surfactants include, without limitation, poloxamers, polyoxyethylene sorbitan esters, fatty alcohol ethoxylates, alkylphenol ethoxylates, tertiary amine oxides, tertiary phosphine oxides, and dialkyl sulfoxides.
  • Suitable amphoteric surfactants include, without limitation, derivatives of C 8-20 aliphatic secondary and tertiary amines having an anionic group such as a carboxylate, sulfate, sulfonate, phosphate or phosphonate.
  • An example of a suitable amphoteric surfactant is cocoamidopropyl betaine.
  • One or more surfactants are optionally present in a total amount of about 0.01-10 wt% (e.g., about 0.05-5.0 wt% or about 0.1-2.0 wt%), for example, in the disclosed oral care composition.
  • An abrasive suitable for use in an oral care composition herein may include, for example, silica (e.g., silica gel, hydrated silica, precipitated silica), alumina, insoluble phosphates, calcium carbonate, and resinous abrasives (e.g., a urea-formaldehyde condensation product).
  • silica e.g., silica gel, hydrated silica, precipitated silica
  • alumina e.g., insoluble phosphates, calcium carbonate
  • resinous abrasives e.g., a urea-formaldehyde condensation product
  • insoluble phosphates useful as abrasives herein are orthophosphates, polymetaphosphates and pyrophosphates, and include dicalcium orthophosphate dihydrate, calcium pyrophosphate, beta-calcium pyrophosphate, tricalcium phosphate, calcium polymetaphosphate and insoluble sodium polymeta
  • One or more abrasives are optionally present in a total amount of about 5-70 wt% (e.g., about 10-56 wt% or about 15-30 wt%), for example, in the disclosed oral care composition.
  • the average particle size of an abrasive in certain embodiments is about 0.1-30 microns (e.g., about 1-20 microns or about 5-15 microns).
  • An oral care composition in certain embodiments may comprise at least one pH-modifying agent.
  • pH-modifying agents may be selected to acidify, make more basic, or buffer the pH of a composition to a pH range of about 2-10 (e.g., pH ranging from about 2-8, 3-9, 4-8, 5-7, 6-10, or 7-9).
  • pH-modifying agents useful herein include, without limitation, carboxylic, phosphoric and sulfonic acids; acid salts (e.g., monosodium citrate, disodium citrate, monosodium malate); alkali metal hydroxides (e.g.
  • sodium hydroxide carbonates such as sodium carbonate, bicarbonates, sesquicarbonates); borates; silicates; phosphates (e.g., monosodium phosphate, trisodium phosphate, pyrophosphate salts); and imidazole.
  • a foam modulator suitable for use in an oral care composition herein may be a polyethylene glycol (PEG), for example.
  • PEG polyethylene glycol
  • High molecular weight PEGs are suitable, including those having an average molecular weight of about 200000-7000000 (e.g., about 500000-5000000 or about 1000000-2500000), for example.
  • One or more PEGs are optionally present in a total amount of about 0.1-10 wt% (e.g. about 0.2-5.0 wt% or about 0.25-2.0 wt%), for example, in the disclosed oral care composition.
  • An oral care composition in certain embodiments may comprise at least one humectant.
  • a humectant in certain embodiments may be a polyhydric alcohol such as glycerin, sorbitol, xylitol, or a low molecular weight PEG. Most suitable humectants also may function as a sweetener herein.
  • One or more humectants are optionally present in a total amount of about 1.0-70 wt% (e.g., about 1.0-50 wt%, about 2-25 wt%, or about 5-15 wt%), for example, in the disclosed oral care composition.
  • a natural or artificial sweetener may optionally be comprised in an oral care composition herein.
  • suitable sweeteners include dextrose, sucrose, maltose, dextrin, invert sugar, mannose, xylose, ribose, fructose, levulose, galactose, corn syrup (e.g., high fructose corn syrup or corn syrup solids), partially hydrolyzed starch, hydrogenated starch hydrolysate, sorbitol, mannitol, xylitol, maltitol, isomalt, aspartame, neotame, saccharin and salts thereof, dipeptide-based intense sweeteners, and cyclamates.
  • One or more sweeteners are optionally present in a total amount of about 0.005-5.0 wt%, for example, in the disclosed oral care composition.
  • a natural or artificial flavorant may optionally be comprised in an oral care composition herein.
  • suitable flavorants include vanillin; sage; marjoram; parsley oil; spearmint oil; cinnamon oil; oil of wintergreen (methylsalicylate); peppermint oil; clove oil; bay oil; anise oil; eucalyptus oil; citrus oils; fruit oils; essences such as those derived from lemon, orange, lime, grapefruit, apricot, banana, grape, apple, strawberry, cherry, or pineapple; bean- and nut-derived flavors such as coffee, cocoa, cola, peanut, or almond; and adsorbed and encapsulated flavorants.
  • ingredients that provide fragrance and/or other sensory effect in the mouth including cooling or warming effects.
  • Such ingredients include, without limitation, menthol, menthyl acetate, menthyl lactate, camphor, eucalyptus oil, eucalyptol, anethole, eugenol, cassia, oxanone, Irisone ® , propenyl guaiethol, thymol, linalool, benzaldehyde, cinnamaldehyde, N-ethyl-p-menthan-3-carboxamine, N,2,3-trimethyl-2-isopropylbutanamide, 3-(1-menthoxy)-propane-1,2-diol, cinnamaldehyde glycerol acetal (CGA), and menthone glycerol acetal (MGA).
  • One or more flavorants are optionally present in a total amount of about 0.01-5.0 wt% (e.g., about 0.1-2.5 wt%), for example,
  • An oral care composition in certain embodiments may comprise at least one whitening agent and/or colorant.
  • a suitable whitening agent is a peroxide compound such as any of those disclosed in U.S. Patent No. 8540971 .
  • Suitable colorants herein include pigments, dyes, lakes and agents imparting a particular luster or reflectivity such as pearling agents, for example.
  • Specific examples of colorants useful herein include talc; mica; magnesium carbonate; calcium carbonate; magnesium silicate; magnesium aluminum silicate; silica; titanium dioxide; zinc oxide; red, yellow, brown and black iron oxides; ferric ammonium ferrocyanide; manganese violet; ultramarine; titaniated mica; and bismuth oxychloride.
  • One or more colorants are optionally present in a total amount of about 0.001-20 wt% (e.g., about 0.01-10 wt% or about 0.1-5.0 wt%), for example, in the disclosed oral care composition.
  • Additional components that can optionally be included in an oral composition herein include one or more enzymes (above), vitamins, and anti-adhesion agents, for example.
  • vitamins useful herein include vitamin C, vitamin E, vitamin B5, and folic acid.
  • suitable anti-adhesion agents include solbrol, ficin, and quorum-sensing inhibitors.
  • the disclosed invention also concerns a method for increasing the viscosity of an aqueous composition.
  • This method comprises contacting one or more poly alpha-1 ,3-glucan ether compounds disclosed herein with the aqueous composition. This step results in increasing the viscosity of the aqueous composition.
  • the poly alpha-1 ,3-glucan ether compound(s) used in this method can be represented by the structure:
  • n can be at least 6, and each R can independently be an H or an organic group.
  • the poly alpha-1,3-glucan ether compound has a degree of substitution of about 0.05 to about 3.0. Any hydrocolloid and aqueous solution disclosed herein can be produced using this method.
  • the contacting step can be performed by mixing or dissolving a poly alpha-1,3-glucan ether compound(s) disclosed herein in the aqueous composition by any means known in the art.
  • mixing or dissolving can be performed manually or with a machine (e.g., industrial mixer or blender, orbital shaker, stir plate, homogenizer, sonicator, bead mill).
  • Mixing or dissolving can comprise a homogenization step in certain embodiments.
  • Homogenization (as well as any other type of mixing) can be performed for about 5 to 60, 5 to 30, 10 to 60, 10 to 30, 5 to 15, or 10 to 15 seconds (or any integer between 5 and 60 seconds), or longer periods of time as necessary to mix a poly alpha-1,3-glucan ether compound with the aqueous composition.
  • a homogenizer can be used at about 5000 to 30000 rpm, 10000 to 30000 rpm, 15000 to 30000 rpm, 15000 to 25000 rpm, or 20000 rpm (or any integer between 5000 and 30000 rpm), for example.
  • Hydrocolloids and aqueous solutions disclosed herein prepared using a homogenization step can be termed as homogenized hydrocolloids and aqueous solutions.
  • Non-limiting examples of fabric types herein include fabrics made of (i) cellulosic fibers such as cotton (e.g., broadcloth, canvas, chambray, chenille, chintz, corduroy, cretonne, damask, denim, flannel, gingham, jacquard, knit, matelassé, oxford, percale, poplin, plissé, sateen, seersucker, sheers, terry cloth, twill, velvet), rayon (e.g., viscose, modal, lyocell), linen, and Tencel ® ; (ii) proteinaceous fibers such as silk, wool and related mammalian fibers; (iii) synthetic fibers such as polyester, acrylic, nylon, and the like; (iv) long vegetable fibers from jute, flax, ramie, coir, kapok, sisal, henequen, abaca, hemp and sunn; and (v) any combination
  • an anionic poly alpha-1,3-glucan ether compound e.g., carboxyalkyl poly alpha-1,3-glucan such as carboxymethyl poly alpha-1,3-glucan
  • material comprising natural fiber (e.g. cotton) and/or synthetic fiber (e.g., polyester).
  • Such adsorption of an anionic poly alpha-1,3-glucan ether compound can be at least about 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, 120%, 140%, 160%, 180%, or 200% greater than the adsorption of the same glucan ether to a cotton fabric (e.g., cretonne), for example.
  • Adsorption of a poly alpha-1,3-glucan ether compound to a fabric herein can be measured following the methodology disclosed in the below Examples, for example.
  • adsorption can be measured using a colorimetric technique (e.g., Dubois et al., 1956, Anal. Chem. 28:350-356 ; Zemlji ⁇ et al., 2006, Lenzinger Berichte 85:68-76) or any other method known in the art.
  • a treatment method in certain embodiments can be considered an oral care method or dental care method, for example.
  • Conditions (e.g., time, temperature) for contacting an oral surface with an aqueous composition herein should be suitable for the intended purpose of making such contact.
  • Other surfaces that can be contacted in a treatment method also include a surface of the integumentary system such as skin, hair or nails.
  • certain embodiments of the disclosed invention concern material (e.g., fabric) that comprises a poly alpha-1,3-glucan ether compound herein.
  • material e.g., fabric
  • Such material can be produced following a material treatment method as disclosed, for example.
  • a material may comprise a glucan ether compound in certain embodiments if the compound is adsorbed to, or otherwise in contact with, the surface of the material.
  • An aqueous composition used in a treatment method herein can be any aqueous composition disclosed herein, such as in the above embodiments or in the below Examples.
  • the poly alpha-1,3-glucan ether component(s) of an aqueous composition can be any as disclosed herein.
  • aqueous compositions include detergents (e.g., laundry detergent or dish detergent) and water-containing dentifrices such as toothpaste.
  • Poly alpha-1,3-glucan ether compounds useful for preparing the hydrocolloids and aqueous solutions of the present invention can be prepared as disclosed in U.S. Patent Appl. Publ. No. 2014/0179913 , and as disclosed herein, for example.
  • alkali hydroxides can be used, such as sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, and/or tetraethylammonium hydroxide.
  • concentration of alkali hydroxide in a preparation with poly alpha-1,3-glucan and a solvent can be from about 1-70 wt%, 5-50 wt%, 10-50 wt%, 10-40 wt%, or 10-30 wt% (or any integer between 1 and 70 wt%).
  • the concentration of alkali hydroxide such as sodium hydroxide can be at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 wt%.
  • An alkali hydroxide used to prepare alkaline conditions may be in a completely aqueous solution or an aqueous solution comprising one or more water-soluble organic solvents such as ethanol or isopropanol.
  • an alkali hydroxide can be added as a solid to provide alkaline conditions.
  • organic solvents that can optionally be included when preparing the reaction include alcohols, acetone, dioxane, isopropanol and toluene, for example; none of these solvents dissolve poly alpha-1,3-glucan. Toluene or isopropanol can be used in certain embodiments. An organic solvent can be added before or after addition of alkali hydroxide.
  • the concentration of an organic solvent (e.g., isopropanol or toluene) in a preparation comprising poly alpha-1,3-glucan and an alkali hydroxide can be at least about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 wt% (or any integer between 10 and 90 wt%).
  • an organic solvent e.g., isopropanol or toluene
  • solvents that can dissolve poly alpha-1,3-glucan can be used when preparing the reaction.
  • solvents include, but are not limited to, lithium chloride(LiCI)/N,N-dimethyl-acetamide (DMAc), SO 2 /diethylamine (DEA)/dimethyl sulfoxide (DMSO), LiCI/1,3-dimethy-2-imidazolidinone (DMI), N,N-dimethylformamide (DMF)/N 2 O 4 , DMSO/tetrabutyl-ammonium fluoride trihydrate (TBAF), N-methylmorpholine-N-oxide (NMMO), Ni(tren)(OH) 2 [tren1 ⁇ 4tris(2-aminoethyl)amine] aqueous solutions and melts of LiClO 4 ⁇ 3H 2 O, NaOH/urea aqueous solutions, aqueous sodium hydroxide, aqueous potassium hydroxide, formic acid, and ionic liquid
  • Poly alpha-1,3-glucan can be contacted with a solvent and one or more alkali hydroxides by mixing. Such mixing can be performed during or after adding these components with each other. Mixing can be performed by manual mixing, mixing using an overhead mixer, using a magnetic stir bar, or shaking, for example. In certain embodiments, poly alpha-1,3-glucan can first be mixed in water or an aqueous solution before it is mixed with a solvent and/or alkali hydroxide.
  • the resulting composition can optionally be maintained at ambient temperature for up to 14 days.
  • ambient temperature refers to a temperature between about 15-30 °C or 20-25 °C (or any integer between 15 and 30 °C).
  • the composition can be heated with or without reflux at a temperature from about 30 °C to about 150 °C (or any integer between 30 and 150 °C) for up to about 48 hours.
  • the composition in certain embodiments can be heated at about 55 °C for about 30 minutes or 60 minutes.
  • composition obtained from mixing a poly alpha-1,3-glucan, solvent, and one or more alkali hydroxides with each other can be heated at about 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, or 60 °C for about 30-90 minutes.
  • the resulting composition can optionally be filtered (with or without applying a temperature treatment step).
  • filtration can be performed using a funnel, centrifuge, press filter, or any other method and/or equipment known in the art that allows removal of liquids from solids. Though filtration would remove much of the alkali hydroxide, the filtered poly alpha-1,3-glucan would remain alkaline (i.e., mercerized poly alpha-1,3-glucan), thereby providing alkaline conditions.
  • An etherification agent comprising an organic group can be contacted with poly alpha-1,3-glucan in a reaction under alkaline conditions in a method herein of producing poly alpha-1,3-glucan ether compounds.
  • an etherification agent can be added to a composition prepared by contacting poly alpha-1,3-glucan, solvent, and one or more alkali hydroxides with each other as described above.
  • an etherification agent can be included when preparing the alkaline conditions (e.g., an etherification agent can be mixed with poly alpha-1,3-glucan and solvent before mixing with alkali hydroxide).
  • An etherification agent herein refers to an agent that can be used to etherify one or more hydroxyl groups of the glucose units of poly alpha-1,3-glucan with an organic group as defined above. Examples of such organic groups include alkyl groups, hydroxy alkyl groups, and carboxy alkyl groups. One or more etherification agents may be used in the reaction.
  • Etherification agents suitable for preparing an alkyl poly alpha-1,3-glucan ether compound include, for example, dialkyl sulfates, dialkyl carbonates, alkyl halides (e.g., alkyl chloride), iodoalkanes, alkyl triflates (alkyl trifluoromethanesulfonates) and alkyl fluorosulfonates.
  • alkyl halides e.g., alkyl chloride
  • iodoalkanes alkyl triflates (alkyl trifluoromethanesulfonates) and alkyl fluorosulfonates.
  • examples of etherification agents for producing methyl poly alpha-1,3-glucan ethers include dimethyl sulfate, dimethyl carbonate, methyl chloride, iodomethane, methyl triflate and methyl fluorosulfonate.
  • Examples of etherification agents for producing ethyl poly alpha-1,3-glucan ethers include diethyl sulfate, diethyl carbonate, ethyl chloride, iodoethane, ethyl triflate and ethyl fluorosulfonate.
  • Examples of etherification agents for producing propyl poly alpha-1,3-glucan ethers include dipropyl sulfate, dipropyl carbonate, propyl chloride, iodopropane, propyl triflate and propyl fluorosulfonate.
  • Examples of etherification agents for producing butyl poly alpha-1,3-glucan ethers include dibutyl sulfate, dibutyl carbonate, butyl chloride, iodobutane and butyl triflate.
  • Etherification agents suitable for preparing a hydroxyalkyl poly alpha-1,3-glucan ether compound include, for example, alkylene oxides such as ethylene oxide, propylene oxide (e.g., 1,2-propylene oxide), butylene oxide (e.g., 1,2-butylene oxide; 2,3-butylene oxide; 1,4-butylene oxide), or combinations thereof.
  • propylene oxide can be used as an etherification agent for preparing hydroxypropyl poly alpha-1,3-glucan
  • ethylene oxide can be used as an etherification agent for preparing hydroxyethyl poly alpha-1,3-glucan.
  • hydroxyalkyl halides e.g., hydroxyalkyl chloride
  • hydroxyalkyl halides can be used as etherification agents for preparing hydroxyalkyl poly alpha-1,3-glucan.
  • hydroxyalkyl halides include hydroxyethyl halide, hydroxypropyl halide (e.g., 2-hydroxypropyl chloride, 3-hydroxypropyl chloride) and hydroxybutyl halide.
  • alkylene chlorohydrins can be used as etherification agents for preparing hydroxyalkyl poly alpha-1,3-glucan.
  • Alkylene chlorohydrins that can be used include, but are not limited to, ethylene chlorohydrin, propylene chlorohydrin, butylene chlorohydrin, or combinations of these.
  • Etherification agents suitable for preparing a dihydroxyalkyl poly alpha-1,3-glucan ether compound include dihydroxyalkyl halides (e.g., dihydroxyalkyl chloride) such as dihydroxyethyl halide, dihydroxypropyl halide (e.g., 2,3-dihydroxypropyl chloride [i.e., 3-chloro-1,2-propanediol]), or dihydroxybutyl halide, for example.
  • dihydroxyalkyl halides e.g., dihydroxyalkyl chloride
  • dihydroxypropyl halide e.g., 2,3-dihydroxypropyl chloride [i.e., 3-chloro-1,2-propanediol]
  • dihydroxybutyl halide e.g., 2,3-dihydroxypropyl chloride
  • 2,3-dihydroxypropyl chloride can be used to prepare dihydroxypropyl poly alpha-1,3-glucan, for
  • Etherification agents suitable for preparing a carboxyalkyl poly alpha-1,3-glucan ether compound may include haloalkylates (e.g., chloroalkylate).
  • haloalkylates include haloacetate (e.g., chloroacetate), 3-halopropionate (e.g., 3-chloropropionate) and 4-halobutyrate (e.g., 4-chlorobutyrate).
  • chloroacetate dichloroacetate
  • sodium chloroacetate or chloroacetic acid can be used as an etherification agent to prepare carboxymethyl poly alpha-1,3-glucan.
  • two or more different etherification agents When producing a poly alpha-1,3-glucan ether compound with two or more different organic groups, two or more different etherification agents would be used, accordingly.
  • both an alkylene oxide and an alkyl chloride could be used as etherification agents to produce an alkyl hydroxyalkyl poly alpha-1,3-glucan ether.
  • Any of the etherification agents disclosed herein may therefore be combined to produce poly alpha-1,3-glucan ether compounds with two or more different organic groups.
  • Such two or more etherification agents may be used in the reaction at the same time, or may be used sequentially in the reaction. When used sequentially, any of the temperature-treatment (e.g., heating) steps disclosed below may optionally be used between each addition.
  • the amount of etherification agent to be contacted with poly alpha-1,3-glucan in a reaction under alkaline conditions can be determined based on the degree of substitution required in the poly alpha-1,3-glucan ether compound being produced.
  • the amount of ether substitution groups on each monomeric unit in poly alpha-1,3-glucan ether compounds produced herein can be determined using nuclear magnetic resonance (NMR) spectroscopy.
  • the molar substitution (MS) value for poly alpha-1,3-glucan has no upper limit.
  • an etherification agent can be used in a quantity of at least about 0.05 mole per mole of poly alpha-1,3-glucan. There is no upper limit to the quantity of etherification agent that can be used.
  • Reactions for producing poly alpha-1,3-glucan ether compounds herein can optionally be carried out in a pressure vessel such as a Parr reactor, an autoclave, a shaker tube or any other pressure vessel well known in the art.
  • a shaker tube is used to perform the reaction in certain embodiments.
  • a reaction herein can optionally be heated following the step of contacting poly alpha-1,3-glucan with an etherification agent under alkaline conditions.
  • the reaction temperatures and time of applying such temperatures can be varied within wide limits.
  • a reaction can optionally be maintained at ambient temperature for up to 14 days.
  • a reaction can be heated, with or without reflux, between about 25 °C to about 200 °C (or any integer between 25 and 200 °C).
  • Reaction time can be varied correspondingly: more time at a low temperature and less time at a high temperature.
  • a reaction in certain embodiments of producing hydroxypropyl poly alpha-1,3-glucan, can be heated to about 75 °C for about 3 hours.
  • a reaction for preparing hydroxyethyl poly alpha-1,3-glucan can be heated to about 60 °C for about 6 hours, for example.
  • a reaction for preparing a hydroxyalkyl poly alpha-1,3-glucan herein can optionally be heated to about 55 °C to about 80 °C (or any integer between 55 and 80 °C) for about 2 hours to about 7 hours, for example.
  • a reaction in certain embodiments of producing carboxymethyl poly alpha-1,3-glucan, can be heated to about 55 °C for about 3 hours.
  • a reaction for preparing a carboxyalkyl poly alpha-1,3-glucan herein can be heated to about 50 °C to about 60 °C (or any integer between 50 and 60 °C) for about 2 hours to about 5 hours, for example.
  • poly alpha-1,3 glucan is added to an alkali hydroxide solution (e.g., tetraethylammonium hydroxide) (e.g., about 20 wt% solution) to a final concentration or mass contribution of poly alpha-1,3 glucan of about 4, 5, 6, 7, or 8 wt% (e.g., ⁇ 6.5 wt%).
  • alkali hydroxide solution e.g., tetraethylammonium hydroxide
  • an appropriate etherification agent e.g., a dihydroxyalkyl chloride such as 2,3-dihydroxypropyl chloride
  • a final concentration of about 7, 8, 9, 10, or 11 wt% e.g., ⁇ 9.5 wt%.
  • the resulting reaction can be held at about 50 °C to about 60 °C (or any integer between 50 and 60 °C, e.g., 55 °C) for about 1.5-2.5 hours (e.g. about 2 hours), for example, before neutralizing the reaction.
  • Water-soluble dihydroxyalkyl poly alpha-1,3-glucan can be produced by employing these steps.
  • a reaction herein can be maintained under an inert gas, with or without heating.
  • inert gas refers to a gas which does not undergo chemical reactions under a set of given conditions, such as those disclosed for preparing a reaction herein.
  • a poly alpha-1,3-glucan ether compound produced in a reaction herein can optionally be washed one or more times with a liquid that does not readily dissolve the compound.
  • poly alpha-1,3-glucan ether can be washed with water, alcohol, acetone, aromatics, or any combination of these, depending on the solubility of the ether compound therein (where lack of solubility is desirable for washing).
  • a solvent comprising an organic solvent such as alcohol is preferred for washing a poly alpha-1,3-glucan ether.
  • a poly alpha-1,3-glucan ether product can be washed one or more times with an aqueous solution containing methanol or ethanol, for example.
  • 70-95 wt% ethanol can be used to wash the product.
  • a poly alpha-1,3-glucan ether product can be washed with a methanol:acetone (e.g., 60:40) solution in another embodiment.
  • Hot water (about 95-100 °C) can be used in certain embodiments, such as for washing alkyl poly alpha-1,3-glucan ethers (e.g., ethyl poly alpha-1,3-glucan) and alkyl hydroxyalkyl poly alpha-1,3-glucan ethers (e.g., ethyl hydroxyethyl poly alpha-1,3-glucan).
  • a poly alpha-1,3-glucan ether produced in the disclosed reaction can be isolated. This step can be performed before or after neutralization and/or washing steps using a funnel, centrifuge, press filter, or any other method or equipment known in the art that allows removal of liquids from solids. For example, a Buchner funnel may be used to isolate a poly alpha-1,3-glucan ether product.
  • An isolated poly alpha-1,3-glucan ether product can be dried using any method known in the art, such as vacuum drying, air drying, or freeze drying.
  • poly alpha-1,3-glucan has less than about 50%, 40%, 30%, 20%, 10%, 5%, 4%, 3%, 2%, 1%, or 0% (or any integer value between 0% and 50%) of glycosidic linkages that are not alpha-1,3.
  • Poly alpha-1,3-glucan used to prepare poly alpha-1,3-glucan ether compounds herein is preferably linear/unbranched.
  • poly alpha-1,3-glucan has no branch points or less than about 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1% branch points as a percent of the glycosidic linkages in the polymer.
  • branch points include alpha-1,6 branch points.
  • the M n or M w of poly alpha-1,3-glucan used to prepare poly alpha-1,3-glucan ether compounds herein may be at least about 1000 to about 600000.
  • M n or M w can be at least about 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 15000, 20000, 25000, 30000, 35000, 40000, 45000, 50000, 75000, 100000, 150000, 200000, 250000, 300000, 350000, 400000, 450000, 500000, 550000, or 600000 (or any integer between 2000 and 600000), for example.
  • Poly alpha-1,3-glucan used for preparing poly alpha-1,3-glucan ether compounds herein can be enzymatically produced from sucrose using one or more glucosyltransferase (gtf) enzymes.
  • the poly alpha-1,3-glucan product of this enzymatic reaction can be purified before using it to prepare an ether using the disclosed process.
  • a poly alpha-1,3-glucan product of a gtf reaction can be used with little or no processing for preparing poly alpha-1,3-glucan ether compounds.
  • a gtf enzymatic reaction can include, in addition to poly alpha-1,3-glucan itself, various components such as sucrose, one or more gtf enzymes, glucose, fructose, leucrose, buffer, FermaSure ® , soluble oligosaccharides, oligosaccharide primers, bacterial enzyme extract components, borates, sodium hydroxide, hydrochloric acid, cell lysate, proteins and/or nucleic acids.
  • the components of a gtf enzymatic reaction can include, in addition to poly alpha-1,3-glucan itself, sucrose, one or more gtf enzymes, glucose, and fructose, for example.
  • the components of a gtf enzymatic reaction can include, in addition to poly alpha-1,3-glucan itself, sucrose, one or more gtf enzymes, glucose, fructose, leucrose and soluble oligosaccharides (and optionally bacterial enzyme extract components).
  • poly alpha-1,3-glucan when in a slurry as disclosed herein, has not been purified or washed.
  • a slurry represents a gtf enzymatic reaction that is complete or for which an observable amount of poly alpha-1,3-glucan has been produced, which forms a solid since it is insoluble in the aqueous reaction milieu (has pH of 5-7, for example).
  • a poly alpha-1,3-glucan slurry can be prepared by setting up a gtf reaction as disclosed in U.S. Patent No. 7,000,000 or U.S. Patent Appl. Publ. Nos. 2013/0244288 and 2013/0244287 , for example.
  • a poly alpha-1,3-glucan slurry can be entered, for example, into a reaction for producing a carboxyalkyl poly alpha-1,3-glucan such as carboxymethyl poly alpha-1,3-glucan.
  • a wet cake of poly alpha-1,3-glucan can be used directly in any of the above processes for producing a poly alpha-1,3-glucan ether compound disclosed herein.
  • a "wet cake of poly alpha-1,3-glucan” as used herein refers to poly alpha-1,3-glucan that has been separated (e.g., filtered) from a slurry and washed with water or an aqueous solution.
  • a wet cake can be washed at least 1, 2, 3, 4, 5, or more times, for example.
  • the poly alpha-1,3-glucan is not dried when preparing a wet cake.
  • a wet cake is termed as "wet” given the retention of water by the washed poly alpha-1,3-glucan.
  • a crosslinking agent is next dissolved in the poly alpha-1,3-glucan ether solution or mixture.
  • concentration of the crosslinking agent in the resulting solution can be about 0.2 to 20 wt%, or about 0.1, 0.2, 0.3, 0.4, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, or 20 wt%.
  • Poly alpha-1,3-glucan was prepared using a gtfJ enzyme preparation as described in U.S. Patent Appl. Publ. No. 2013/0244288 .
  • This Example describes producing the glucan ether derivative, hydroxypropyl poly alpha-1,3-glucan.
  • This Example describes producing the glucan ether derivative, hydroxyethyl poly alpha-1,3-glucan.
  • the solids were filtered using a Buchner funnel with 35-micrometer filter paper. The solids were then washed in a beaker by adding a methanol:acetone (60:40 v/v) mixture and stirring with a stir bar for 20 minutes. The methanol:acetone mixture was then filtered away from the solids. This washing step was repeated two times. The solids, which had a slightly brown/beige color, were dried in a vacuum oven with a nitrogen bleed. The hydroxyethyl poly alpha-1,3-glucan product was soluble in a 10% NaOH solution. The MS of the dried product was reported by NMR to be 0.72.
  • This Example describes producing the glucan ether derivative, ethyl poly alpha-1,3-glucan.
  • Poly alpha-1,3-glucan is added to a shaker tube, after which sodium hydroxide (1-70% solution) and ethyl chloride are added to provide a reaction.
  • the reaction is heated to 25-200 °C and held at that temperature for 1-48 hours before the reaction is neutralized with acetic acid.
  • the solid thus formed is collected by vacuum filtration and washed, dried under a vacuum at 20-25 °C, and analyzed by NMR and SEC to determine the molecular weight and degree of substitution (DoS) of the ethyl poly alpha-1,3-glucan.
  • DoS molecular weight and degree of substitution
  • glucan ether derivative ethyl poly alpha-1,3-glucan
  • This Example describes producing the glucan ether derivative, ethyl hydroxyethyl poly alpha-1,3-glucan.
  • Poly alpha-1,3-glucan is added to a shaker tube, after which sodium hydroxide (1-70% solution) is added. Then, ethyl chloride is added followed by an ethylene oxide/ethyl chloride mixture to provide a reaction. The reaction is slowly heated to 25-200 °C and held at that temperature for 1-48 hours before being neutralized with acetic acid. The solid thus formed is collected by vacuum filtration and washed with hot water, dried under a vacuum at 20-70 °C, and analyzed by NMR and SEC to determine the molecular weight and DoS of the ethyl hydroxyethyl poly alpha-1,3-glucan.
  • the glucan ether derivative ethyl hydroxyethyl poly alpha-1,3-glucan
  • This Example describes producing the glucan ether derivative, methyl poly alpha-1,3-glucan.
  • the resulting methyl poly alpha-1,3-glucan solid was filtered and neutralized with 20 mL 90% acetic acid, followed by three 200-mL ethanol washes. NMR analysis was performed, indicating that the DoS of the methyl poly alpha-1,3-glucan product was 1.2.
  • Table 1 provides a list of DoS measurements for various samples of methyl poly alpha-1,3-glucan prepared using methods having certain modifications compared to the above method (refer to Table 1).
  • the mercerization step alkali treatment of poly alpha-1,3-glucan prior to addition of methylating reagent
  • Table 1 was conducted for 1 hour, as above.
  • glucan ether derivative methyl poly alpha-1,3-glucan
  • This Example describes producing water-soluble methyl poly alpha-1,3-glucan.
  • a solution of the methyl poly alpha-1,3-glucan product in water was prepared by dissolving 0.2 g of the product in 9.8 g water and mixing at room temperature. A clear solution was formed thereby indicating that the methyl poly alpha-1,3-glucan product was water-soluble.
  • water-soluble methyl poly alpha-1,3-glucan was prepared and isolated.
  • This Example describes producing the glucan ether derivative, hydroxyalkyl methyl poly alpha-1,3-glucan.
  • Poly alpha-1,3-glucan is added to a vessel, after which sodium hydroxide (5-70% solution) is added. This preparation is stirred for 0.5-8 hours. Then, methyl chloride is added to the vessel to provide a reaction, which is then heated to 30-100 °C for up to 14 days. An alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene oxide, etc.) is then added to the reaction while controlling the temperature. The reaction is heated to 25-100 °C for up to 14 days before being neutralized with acid. The solid product thus formed is filtered, washed and dried.
  • sodium hydroxide 5-70% solution
  • methyl chloride is added to the vessel to provide a reaction, which is then heated to 30-100 °C for up to 14 days.
  • An alkylene oxide e.g., ethylene oxide, propylene oxide, butylene oxide, etc.
  • the reaction is heated to 25-100 °C for up to 14 days before being neutralized with acid.
  • the glucan ether derivative hydroxyalkyl methyl poly alpha-1,3-glucan
  • hydroxyalkyl methyl poly alpha-1,3-glucan is prepared and isolated.
  • this derivative include hydroxyethyl methyl poly alpha-1,3-glucan, hydroxypropyl methyl poly alpha-1,3-glucan, and hydroxybutyl methyl poly alpha-1,3-glucan.
  • This Example describes producing the glucan ether derivative, carboxymethyl hydroxyethyl poly alpha-1,3-glucan.
  • the glucan ether derivative carboxymethyl hydroxyethyl poly alpha-1,3-glucan, is prepared and isolated.
  • This Example describes producing the glucan ether derivative, sodium carboxymethyl hydroxyethyl poly alpha-1,3-glucan.
  • Poly alpha-1,3-glucan is added to an aliquot of an alcohol such as isopropanol in a 400-mL capacity shaker tube, after which sodium hydroxide (1-70% solution) is added. This preparation is stirred for up to 48 hours. Then, sodium monochloroacetate is added to provide a reaction, which is then heated to 25-100 °C for up to 14 days. Ethylene oxide is then added to the reaction, which is then heated to 25-100 °C for up to 14 days before being neutralized with acid (e.g., acetic, sulfuric, nitric, hydrochloric, etc.). The solid product thus formed is collected by vacuum filtration, washed and dried.
  • an alcohol such as isopropanol
  • sodium hydroxide (1-70% solution
  • This preparation is stirred for up to 48 hours.
  • sodium monochloroacetate is added to provide a reaction, which is then heated to 25-100 °C for up to 14 days.
  • Ethylene oxide is
  • the glucan ether derivative sodium carboxymethyl hydroxyethyl poly alpha-1,3-glucan, is prepared and isolated.
  • This Example describes producing the glucan ether derivative, carboxymethyl hydroxypropyl poly alpha-1,3-glucan.
  • glucan ether derivative carboxymethyl hydroxypropyl poly alpha-1,3-glucan
  • This Example describes producing the glucan ether derivative, sodium carboxymethyl hydroxypropyl poly alpha-1,3-glucan.
  • Table 2 provides a list of DoS measurements for various samples of sodium carboxymethyl poly alpha-1,3-glucan prepared using the above method.
  • the poly alpha-1,3-glucan starting material had various molecular weights (Table 2).
  • Table 2 DoS of Sodium Carboxymethyl Poly Alpha-1,3-Glucan Prepared from Poly Alpha-1,3-Glucan CMG Sample Designation M w of poly alpha-1,3-glucan starting material DoS 1A (35) 140287 0.5 1B (36) 140287 0.9 1C (39) 140287 1 1D (44) 88445 0.7 1E (47) 278858 0.7 1F (58) 248006 1G (67) 236854 0.5 1H (72) 236854 0.9 1I (-41) 200000 0.5 1J (-39) 168584 0.5
  • a second solution of 2 wt% CMG (1G, Table 2) was prepared as in Example 16 using the homogenization method. The solution was divided into two aliquots. One aliquot was adjusted to pH 3.0 using citric acid and the second aliquot was adjusted to pH 12 using sodium hydroxide.
  • This Example describes the effect of sucrose on the viscosity of CMG in solution.
  • KNaCMG samples were subjected to various shear rates using a Brookfield III+ Rheometer equipped with a recirculating bath to control temperature (20 °C) and a YULA15-E(Z) spindle.
  • the shear rate was increased using a gradient program which increased from 0.01-250 rpm and the shear rate was increased by 7.36 (1/s) every 20 seconds.
  • the results of this experiment are listed in Table 12.
  • LiNaCMG samples were subjected to various shear rates using a Brookfield III+ Rheometer equipped with a recirculating bath to control temperature (20 °C) and a YULA15-E(Z) spindle.
  • the shear rate was increased using a gradient program which increased from 0.01-250 rpm and the shear rate was increased by 7.36 (1/s) every 20 seconds.
  • the results of this experiment are listed in Table 14.
  • LiNaCMG when dissolved in an aqueous solution not only modifies the viscosity of the solution, but also the rheological properties of the solution. LiNaCMG can therefore be added to an aqueous liquid to modify its rheological profile.
  • LiCMG lithium carboxymethyl poly alpha-1,3-glucan
  • This Example describes producing the glucan ether derivative, methyl poly alpha-1,3-glucan (MG). This Example is in addition to Examples 5 and 6, which describe producing MG.
  • the reaction was held at temperature for 17 hours and then charged with an additional 20 g of methyl chloride and held at temperature for 17 hours. After cooling, the reaction was neutralized with 90% acetic acid.
  • the solid from this reaction was collected by vacuum filtration, washed with methanol three times, dried under vacuum at 20-25 °C, and analyzed by NMR to determine DoS. The solid material obtained was identified as MG with a DoS of 1.75.
  • the solid was collected by vacuum filtration and washed with methanol:acetone (60:40) five times, dried under vacuum at 20-25 °C, and analyzed by NMR to determine DoS.
  • the solid material obtained was identified as MG with a DoS of 1.8. This MG was denoted as Sample 1.
  • the solid was collected by vacuum filtration and washed with methanol:acetone (60:40) five times, dried under vacuum at 20-25 °C, and analyzed by NMR to determine DoS.
  • the solid material obtained was identified as MG. This MG was denoted as Sample 2.
  • This Example describes the effect of shear rate on the viscosity of MG. It is shown that MG exhibits shear thinning behavior. Thus, addition of MG to a liquid can modify the rheological behavior of the liquid.
  • MG samples were subjected to 10-250 rpm shear rates using a Brookfield DV III+ Rheometer equipped with a recirculating bath to control temperature (20 °C) and an SC4-21 Thermosel ® spindle or ULA (ultra low adapter) spindle and adapter set.
  • the shear rate was increased using a gradient program which increased from 10-250 rpm.
  • the shear rate was increased by 7.35 (1/s) every 20 seconds for the ULA spindle and adapter, and by 4.9 (1/s) every 20 seconds for the SC4-21 spindle.
  • Table 15 The results of this experiment are listed in Table 15.
  • MG when dissolved in an aqueous solution not only modifies the viscosity of the solution, but also the rheological properties of the solution. MG can therefore be added to an aqueous liquid to modify its rheological profile.
  • glucan ether derivative ethyl poly alpha-1,3-glucan
  • the EG solutions were subjected to various shear rates using a Brookfield DV III+ Rheometer equipped with a recirculating bath to control temperature (20 °C) and an SC4-21 Thermosel ® spindle or ULA spindle and adapter set.
  • the shear rate was increased using a gradient program which increased from 10-250 rpm.
  • the shear rate was increased by 7.35 (1/s) every 20 seconds for the ULA spindle and adapter, and by 4.9 (1/s) every 20 seconds for the SC4-21 spindle.
  • Table 16 The results of this experiment are listed in Table 16.
  • EG when dissolved in an aqueous solution not only modifies the viscosity of the solution, but also the rheological properties of the solution. EG can therefore be added to an aqueous liquid to modify its rheological profile.
  • This Example describes producing the glucan ether derivative, hydroxypropyl poly alpha-1,3-glucan (HPG). This Example is in addition to Example 1, which describes a method for producing HPG.
  • HPG hydroxypropyl poly alpha-1,3-glucan
  • This Example describes producing a dihydroxyalkyl ether derivative of poly alpha-1,3-glucan. Specifically, dihydroxypropyl poly alpha-1,3-glucan was produced.
  • This Example describes producing dihydroxypropyl poly alpha-1,3-glucan. This Example is in addition to Example 34, which also describes producing this glucan ether derivative.
  • 3-chloro-1,2-propanediol (16 g) was then added to provide a reaction (containing ⁇ 9.5 wt% 3-chloro-1,2-propanediol), which was held at 55 °C for 2 hours before being neutralized with acetic acid. After neutralization, an excess of isopropanol was added to precipitate a solid. The solid thus formed was collected by vacuum filtration and washed with ethanol (95%) four times, and dried under vacuum at 20-25 °C. The solid material obtained was identified as dihydroxypropyl poly alpha-1,3-glucan that was water soluble, and having a degree of substitution of 0.6.
  • This Example describes the effect of shear rate on the viscosity of dihydroxypropyl poly alpha-1,3-glucan. It is shown that this glucan ether exhibits shear thinning behavior. Thus, addition of dihydroxypropyl poly alpha-1,3-glucan to a liquid can modify the rheological behavior of the liquid.

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Claims (15)

  1. Hydrokolloid oder wässrige Lösung, umfassend eine Poly-alpha-1,3-glucanether-Verbindung, die durch die folgende Struktur wiedergegeben wird:
    Figure imgb0009
     wobei
    (i) n mindestens 6 ist,
    (ii) R jeweils unabhängig für H oder eine organische Gruppe steht,
    (iii) die Verbindung einen Substitutionsgrad von etwa 0,05 bis etwa 3,0 aufweist,
    (iv) das Hydrokolloid bzw. die wässrige Lösung eine Viskosität von mindestens etwa 10 Centipoise aufweist und
    (v) die Poly-alpha-1,3-glucanether-Verbindung vernetzt ist.
  2. Hydrokolloid oder wässrige Lösung nach Anspruch 1, wobei mindestens eine organische Gruppe aus der Gruppe bestehend aus Alkyl, Hydroxyalkyl und Carboxyalkyl ausgewählt ist.
  3. Hydrokolloid oder wässrige Lösung nach Anspruch 2, wobei mindestens eine organische Gruppe aus der Gruppe bestehend aus Methyl, Ethyl, Hydroxypropyl, Dihydroxypropyl und Hydroxyethyl ausgewählt ist.
  4. Hydrokolloid oder wässrige Lösung nach Anspruch 2, wobei mindestens eine organische Gruppe Carboxymethyl ist.
  5. Hydrokolloid oder wässrige Lösung nach einem der Ansprüche 1-4, wobei die Verbindung eine Art von organischer Gruppe enthält.
  6. Hydrokolloid oder wässrige Lösung nach einem der Ansprüche 1-4, wobei die Verbindung zwei oder mehr Arten von organischer Gruppe enthält.
  7. Hydrokolloid oder wässrige Lösung nach einem der Ansprüche 1-6, wobei der Substitutionsgrad etwa 0,2 bis etwa 2,0 beträgt.
  8. Hydrokolloid oder wässrige Lösung nach einem der Ansprüche 1-7, wobei der pH-Wert des Hydrokolloids bzw. der wässrigen Lösung zwischen etwa 4,0 bis etwa 8,0 liegt.
  9. Hydrokolloid oder wässrige Lösung nach einem der Ansprüche 1-8, wobei das Hydrokolloid bzw. die wässrige Lösung in Form eines pharmazeutischen Produkts, Lebensmittelprodukts oder technischen Produkts vorliegt.
  10. Hydrokolloid oder wässrige Lösung nach einem der Ansprüche 1-8, wobei das Hydrokolloid bzw. die wässrige Lösung in Form eines Haushaltsprodukts vorliegt.
  11. Hydrokolloid oder wässrige Lösung nach einem der Ansprüche 1-8, wobei das Hydrokolloid bzw. die wässrige Lösung in Form eines Körperpflegeprodukts vorliegt.
  12. Hydrokolloid oder wässrige Lösung nach Anspruch 11, wobei es sich bei dem Körperpflegeprodukt um eine Hautpflegezusammensetzung handelt.
  13. Hydrokolloid oder wässrige Lösung nach Anspruch 11, wobei es sich bei dem Körperpflegeprodukt um eine kosmetische Zusammensetzung handelt.
  14. Hydrokolloid oder wässrige Lösung nach Anspruch 11, wobei es sich bei dem Körperpflegeprodukt um eine Lotion oder eine Salbe handelt.
  15. Hydrokolloid oder wässrige Lösung nach einem der Ansprüche 1-8, wobei das Hydrokolloid bzw. die wässrige Lösung in Form einer Geschirrspülmittelzusammensetzung oder Waschmittelzusammensetzung vorliegt.
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Families Citing this family (56)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3083704B1 (de) 2013-12-16 2022-08-17 Nutrition & Biosciences USA 4, Inc. Verwendung von poly-alpha-1,3-glucan-ethern als viskositätsmodifikatoren
BR112016014014B1 (pt) 2013-12-18 2021-08-10 Nutrition & Biosciences USA 4, Inc. Composição, método para a produção de um composto e método para o tratamento de um material
KR102443837B1 (ko) 2014-01-06 2022-09-19 뉴트리션 앤드 바이오사이언시스 유에스에이 4, 인크. 폴리 알파-1,3-글루칸 필름의 제조
WO2015109066A1 (en) 2014-01-17 2015-07-23 E. I. Du Pont De Nemours And Company Production of poly alpha-1,3-glucan formate films
US9714403B2 (en) 2014-06-19 2017-07-25 E I Du Pont De Nemours And Company Compositions containing one or more poly alpha-1,3-glucan ether compounds
WO2015195777A1 (en) * 2014-06-19 2015-12-23 E. I. Du Pont De Nemours And Company Compositions containing one or more poly alpha-1,3-glucan ether compounds
KR102625499B1 (ko) 2014-12-22 2024-01-17 뉴트리션 앤드 바이오사이언시스 유에스에이 4, 인크. 폴리 알파-1,3-글루칸 함유 폴리머 블렌드
AT518612B1 (de) * 2015-02-06 2019-03-15 Chemiefaser Lenzing Ag Polysaccharid-Suspension, Verfahren zu ihrer Herstellung und ihre Verwendung
KR20170109571A (ko) * 2015-02-06 2017-09-29 이 아이 듀폰 디 네모아 앤드 캄파니 폴리 알파-1,3-글루칸계 폴리머의 콜로이드 분산액
AU2016243411B2 (en) 2015-04-03 2020-10-22 Nutrition & Biosciences USA 4, Inc. Gelling dextran ethers
EP3277100B1 (de) 2015-04-03 2023-09-06 Nutrition & Biosciences USA 4, Inc. Oxidiertes dextran
CN107995923B (zh) 2015-06-01 2021-11-02 营养与生物科学美国4公司 包含聚α-1,3-葡聚糖的胶体分散体的结构化的液体组合物
JP6956013B2 (ja) * 2015-06-01 2021-10-27 ニュートリション・アンド・バイオサイエンシーズ・ユーエスエー・フォー，インコーポレイテッド ポリα−１，３−グルカンフィブリッド及びその使用、並びにポリα−１，３−グルカンフィブリッドを製造する方法
RU2729250C2 (ru) 2015-10-26 2020-08-05 ДЮПОН ИНДАСТРИАЛ БАЙОСАЙЕНСИЗ ЮЭсЭй, ЭлЭлСи Полисахаридные покрытия для бумаги
US10731297B2 (en) 2015-10-26 2020-08-04 Dupont Industrial Biosciences Usa, Llc Water insoluble alpha-(1,3-glucan) composition
WO2017083226A1 (en) * 2015-11-13 2017-05-18 E. I. Du Pont De Nemours And Company Glucan fiber compositions for use in laundry care and fabric care
JP2019504932A (ja) 2015-11-13 2019-02-21 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ 洗濯ケアおよび織物ケアにおいて使用するためのグルカン繊維組成物
EP3374400B1 (de) * 2015-11-13 2022-04-13 Nutrition & Biosciences USA 4, Inc. Glucanfaserzusammensetzungen zur verwendung in der wäsche- und textilpflege
MX2018006273A (es) 2015-11-26 2018-08-16 Du Pont Polipeptidos capaces de producir glucanos que tienen ramificaciones alfa-1,2 y uso de los mismos.
US10895028B2 (en) 2015-12-14 2021-01-19 Dupont Industrial Biosciences Usa, Llc Nonwoven glucan webs
EP3469052B1 (de) * 2016-06-13 2021-10-20 Nutrition & Biosciences USA 4, Inc. Waschmittelzusammensetzungen
EP3541870A1 (de) * 2016-11-16 2019-09-25 E. I. du Pont de Nemours and Company Cellulose/polysaccharid-verbundwerkstoffe
JP7402045B2 (ja) * 2016-12-16 2023-12-20 ニュートリション・アンド・バイオサイエンシーズ・ユーエスエー・フォー，インコーポレイテッド 両親媒性多糖誘導体及びそれを含む組成物
CN111315785B (zh) * 2017-09-11 2023-11-10 营养与生物科学美国4公司 聚α-1,3-葡聚糖化合物
AU2018347551B2 (en) 2017-10-13 2023-09-14 Nutrition & Biosciences USA 4, Inc. Flowable bulk granular polysaccharide
WO2019094357A2 (en) 2017-11-10 2019-05-16 E. I. Du Pont De Nemours And Company Unique morphological polysaccharide
JP2021507955A (ja) * 2017-12-14 2021-02-25 デュポン・インダストリアル・バイオサイエンシーズ・ユーエスエイ・エルエルシー α−１，３−グルカングラフトコポリマー
EP3728466B1 (de) * 2018-02-26 2021-09-15 Nutrition & Biosciences USA 4, Inc. Mischungen aus polyestern und polysacchariden
JP2020037649A (ja) * 2018-09-04 2020-03-12 Dic株式会社 ラミネート用硬化型接着剤、積層フィルム及び包装体
CN113574074B (zh) 2018-10-25 2023-03-21 营养与生物科学美国第四公司 α-1,3-葡聚糖接枝共聚物
AU2020379826A1 (en) 2019-11-06 2022-05-19 Nutrition & Biosciences USA 4, Inc. Highly crystalline alpha-1,3-glucan
JP7409058B2 (ja) * 2019-12-09 2024-01-09 ライオン株式会社 義歯洗浄剤組成物及び泡状義歯洗浄剤製品
WO2021158543A1 (en) 2020-02-04 2021-08-12 Nutrition & Biosciences USA 4, Inc. Aqueous dispersions of insoluble alpha-glucan comprising alpha-1,3 glycosidic linkages
EP3907270A1 (de) * 2020-05-05 2021-11-10 The Procter & Gamble Company Zusammensetzungen mit kationischen poly-alpha-1,3-glucan-ethern
AU2021284362A1 (en) 2020-06-04 2022-12-22 Nutrition & Biosciences USA 4, Inc. Dextran-alpha-glucan graft copolymers and derivatives thereof
WO2021252569A1 (en) 2020-06-10 2021-12-16 Nutrition & Biosciences USA 4, Inc. Poly alpha-1,6-glucan derivatives and compositions comprising same
EP3922703A1 (de) 2020-06-10 2021-12-15 The Procter & Gamble Company Wäschepflege- oder geschirrpflegezusammensetzung mit einem poly-alpha-1,6-glucan-derivat
EP3922704A1 (de) 2020-06-10 2021-12-15 The Procter & Gamble Company Wäschepflege- oder geschirrpflegezusammensetzung mit einem poly-alpha-1,6-glucan-derivat
CA3178408A1 (en) 2020-06-10 2021-12-16 Mark Robert Sivik A laundry care or dish care composition comprising a poly alpha-1,6-glucan derivative
US11732216B2 (en) 2020-06-10 2023-08-22 The Procter & Gamble Company Laundry care or dish care composition comprising a poly alpha-1,6-glucan derivative
EP3922705B1 (de) 2020-06-10 2023-01-25 The Procter & Gamble Company Eine wäsche- oder geschirrpflegezusammensetzung enthaltend ein polyalpha-glucanderivat
US20210395655A1 (en) * 2020-06-18 2021-12-23 The Procter & Gamble Company Water-soluble unit dose article comprising a polyvinylalcohol film and a cationic poly alpha-1,6-glucan ether compound
US20240199766A1 (en) 2021-02-19 2024-06-20 Nutrition & Biosciences USA 4, Inc. Oxidized polysaccharide derivatives
CN117337308A (zh) 2021-05-04 2024-01-02 营养与生物科学美国4公司 包含氧化的不溶性α-葡聚糖的组合物
WO2022235655A1 (en) 2021-05-04 2022-11-10 Nutrition & Biosciences USA 4, Inc. Compositions comprising insoluble alpha-glucan
JP2024525685A (ja) 2021-07-13 2024-07-12 ニュートリション・アンド・バイオサイエンシーズ・ユーエスエー・フォー，インコーポレイテッド カチオン性グルカンエステル誘導体
WO2023081341A1 (en) 2021-11-05 2023-05-11 Nutrition & Biosciences USA 4, Inc. Compositions comprising one cationic alpha- 1,6-glucan derivative and one alpha- 1,3-glucan
WO2023114942A1 (en) 2021-12-16 2023-06-22 Nutrition & Biosciences USA 4, Inc. Compositions comprising cationic alpha-glucan ethers in aqueous polar organic solvents
WO2023137258A1 (en) 2022-01-12 2023-07-20 Nutrition & Biosciences USA 4, Inc. Coating compositions comprising rubber and insoluble alpha-glucan
WO2023183280A1 (en) 2022-03-21 2023-09-28 Nutrition & Biosciences USA 4, Inc. Compositions comprising insoluble alpha-glucan
WO2024015769A1 (en) 2022-07-11 2024-01-18 Nutrition & Biosciences USA 4, Inc. Amphiphilic glucan ester derivatives
WO2024081773A1 (en) 2022-10-14 2024-04-18 Nutrition & Biosciences USA 4, Inc. Compositions comprising water, cationic alpha-1,6-glucan ether and organic solvent
WO2024086560A1 (en) 2022-10-17 2024-04-25 International N&H Denmark Aps Method for improving flavor in plant-based food stuff
WO2024097166A1 (en) 2022-11-02 2024-05-10 Nutrition & Biosciences USA 4, Inc. Compositions comprising xanthan gum and crystalline alpha-1,3-glucan
WO2024112740A1 (en) 2022-11-23 2024-05-30 Nutrition & Biosciences USA 4, Inc. Hygienic treatment of surfaces with compositions comprising hydrophobically modified alpha-glucan derivative
WO2024129953A1 (en) 2022-12-16 2024-06-20 Nutrition & Biosciences USA 4, Inc. Esterification of alpha-glucan comprising alpha-1,6 glycosidic linkages

Family Cites Families (252)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1296839A (de) 1969-05-29 1972-11-22
GB1372034A (en) 1970-12-31 1974-10-30 Unilever Ltd Detergent compositions
JPS5028515B2 (de) 1971-09-30 1975-09-16
SE8001698L (sv) 1980-03-05 1981-09-06 Eka Ab Antiredepositionsmedel
DK187280A (da) 1980-04-30 1981-10-31 Novo Industri As Ruhedsreducerende middel til et fuldvaskemiddel fuldvaskemiddel og fuldvaskemetode
GB2095275B (en) 1981-03-05 1985-08-07 Kao Corp Enzyme detergent composition
US4462917A (en) 1982-09-27 1984-07-31 Halliburton Company Method and compositions for fracturing subterranean formations
US4464270A (en) 1982-09-27 1984-08-07 Halliburton Company Method and compositions for fracturing subterranean formations
US4477360A (en) 1983-06-13 1984-10-16 Halliburton Company Method and compositions for fracturing subterranean formations
US4760025A (en) 1984-05-29 1988-07-26 Genencor, Inc. Modified enzymes and methods for making same
IT1174953B (it) 1983-12-06 1987-07-01 Zanussi A Spa Industrie Macchina lavabiancheria
US5972682A (en) 1984-05-29 1999-10-26 Genencor International, Inc. Enzymatically active modified subtilisins
US5700676A (en) 1984-05-29 1997-12-23 Genencor International Inc. Modified subtilisins having amino acid alterations
US4689297A (en) 1985-03-05 1987-08-25 Miles Laboratories, Inc. Dust free particulate enzyme formulation
WO1987000859A1 (en) 1985-08-09 1987-02-12 Gist-Brocades N.V. Novel lipolytic enzymes and their use in detergent compositions
IT1204219B (it) 1986-03-11 1989-03-01 Zanussi Elettrodomestici Procedimento di trattamento della biancheria e macchina lavabiancheria che realizza tale procedimento
EP0243151B1 (de) 1986-04-22 1992-12-16 Ajinomoto Co., Inc. Modifiziertes, durch Mikroorganismen hergestelltes Zellulose-Gel und sein Komplex mit tierischen Zellen
US4810414A (en) 1986-08-29 1989-03-07 Novo Industri A/S Enzymatic detergent additive
NZ221627A (en) 1986-09-09 1993-04-28 Genencor Inc Preparation of enzymes, modifications, catalytic triads to alter ratios or transesterification/hydrolysis ratios
US5288480A (en) 1987-01-30 1994-02-22 Colgate-Palmolive Co. Antiplaque antibacterial oral composition
EP0322429B1 (de) 1987-05-29 1994-10-19 Genencor International, Inc. Cutinase haltige reinigungsmittelzusammensetzungen
EP0305216B1 (de) 1987-08-28 1995-08-02 Novo Nordisk A/S Rekombinante Humicola-Lipase und Verfahren zur Herstellung von rekombinanten Humicola-Lipasen
JPS6474992A (en) 1987-09-16 1989-03-20 Fuji Oil Co Ltd Dna sequence, plasmid and production of lipase
ATE129523T1 (de) 1988-01-07 1995-11-15 Novo Nordisk As Spezifische protease.
JP3079276B2 (ja) 1988-02-28 2000-08-21 天野製薬株式会社 組換え体ｄｎａ、それを含むシュードモナス属菌及びそれを用いたリパーゼの製造法
EP0406314B1 (de) 1988-03-24 1993-12-01 Novo Nordisk A/S Cellulosezubereitung
US5648263A (en) 1988-03-24 1997-07-15 Novo Nordisk A/S Methods for reducing the harshness of a cotton-containing fabric
US4799550A (en) 1988-04-18 1989-01-24 Halliburton Company Subterranean formation treating with delayed crosslinking gel fluids
US4968443A (en) * 1988-07-22 1990-11-06 Colgate-Palmolive Company Antistatic laundry detergent composition and processes therefor
WO1990009446A1 (en) 1989-02-17 1990-08-23 Plant Genetic Systems N.V. Cutinase
DE69032360T2 (de) 1989-06-29 1998-12-03 Genencor International, Inc., Rochester, N.Y. Mutierte mikrobielle alpha-Amylasen mit erhöhter thermischer, saurer und/oder alkylischer Stabilität
GB8915658D0 (en) 1989-07-07 1989-08-23 Unilever Plc Enzymes,their production and use
FR2656323B1 (fr) * 1989-10-26 1993-01-08 Elf France Emulsion de liant bitumineux a viscosite controlee par addition de scleroglucane.
ES2055601T3 (es) 1990-04-14 1994-08-16 Kali Chemie Ag Lipasas alcalinas de bacillus, secuencias de adn que las codifican, asi como bacilli que producen estas lipasas.
DK115890D0 (da) 1990-05-09 1990-05-09 Novo Nordisk As Enzym
WO1991017243A1 (en) 1990-05-09 1991-11-14 Novo Nordisk A/S A cellulase preparation comprising an endoglucanase enzyme
US5814501A (en) 1990-06-04 1998-09-29 Genencor International, Inc. Process for making dust-free enzyme-containing particles from an enzyme-containing fermentation broth
JPH07119243B2 (ja) * 1990-08-23 1995-12-20 鐘紡株式会社 β−グルカン及びその製造方法
JP3469234B2 (ja) 1990-09-13 2003-11-25 ノボザイムス アクティーゼルスカブ リパーゼ変異体
JP2854136B2 (ja) 1990-09-28 1999-02-03 ザ、プロクター、エンド、ギャンブル、カンパニー 酵素性能を高めるためのポリヒドロキシ脂肪酸アミド界面活性剤
WO1992006221A1 (en) 1990-10-05 1992-04-16 Genencor International, Inc. Methods for treating cotton-containing fabrics with cellulase
EP0495258A1 (de) 1991-01-16 1992-07-22 The Procter & Gamble Company Waschmittelzusammensetzungen mit hochaktiven Cellulasen und Tonweichmachern
US5340735A (en) 1991-05-29 1994-08-23 Cognis, Inc. Bacillus lentus alkaline protease variants with increased stability
DK0551408T4 (da) 1991-06-11 2012-10-22 Genencor Int Detergentsammensætninger, som indeholder cellulasesammensætninger med deficit af CBHI-typekomponenter
US5324649A (en) 1991-10-07 1994-06-28 Genencor International, Inc. Enzyme-containing granules coated with hydrolyzed polyvinyl alcohol or copolymer thereof
DK72992D0 (da) 1992-06-01 1992-06-01 Novo Nordisk As Enzym
DK88892D0 (da) 1992-07-06 1992-07-06 Novo Nordisk As Forbindelse
ATE444356T1 (de) 1992-07-23 2009-10-15 Novozymes As Mutierte -g(a)-amylase, waschmittel und geschirrspülmittel
EP0663950B1 (de) 1992-10-06 2004-03-17 Novozymes A/S Zellulosevarianten
ATE237681T1 (de) 1992-12-01 2003-05-15 Novozymes As Beschleunigung von enzymreaktionen
US5320830A (en) * 1992-12-30 1994-06-14 The Procter & Gamble Company Oral compositions
PL310326A1 (en) 1993-02-11 1995-12-11 Genencor Int Novel oxidation-stable mutants of alpha-amylase as well as detergent and starch liquefaction compositions containing them
DE69434242T2 (de) 1993-04-27 2006-01-12 Genencor International, Inc., Palo Alto Neuartige Lipasevarianten zur Verwendung in Reinigungsmitteln
DK77393D0 (da) 1993-06-29 1993-06-29 Novo Nordisk As Aktivering af enzymer
JP2859520B2 (ja) 1993-08-30 1999-02-17 ノボ ノルディスク アクティーゼルスカブ リパーゼ及びそれを生産する微生物及びリパーゼ製造方法及びリパーゼ含有洗剤組成物
EP0722490B2 (de) 1993-10-08 2013-10-23 Novozymes A/S Amylasevarianten
KR100338786B1 (ko) 1993-10-13 2002-12-02 노보자임스 에이/에스 H2o2-안정한퍼록시다제변이체
JPH07143883A (ja) 1993-11-24 1995-06-06 Showa Denko Kk リパーゼ遺伝子及び変異体リパーゼ
KR970701264A (ko) 1994-02-22 1997-03-17 안네 제케르 지질분해효소의 변이체 제조방법(a method of preparing a viriant of a lipolytic enzyme)
US5691295A (en) 1995-01-17 1997-11-25 Cognis Gesellschaft Fuer Biotechnologie Mbh Detergent compositions
EP1921148B1 (de) 1994-02-24 2011-06-08 Henkel AG & Co. KGaA Verbesserte Enzyme und Detergentien damit
ES2364774T3 (es) 1994-02-24 2011-09-14 HENKEL AG & CO. KGAA Enzimas mejoradas y detergentes que las contienen.
CA2185101A1 (en) 1994-03-08 1995-09-14 Martin Schulein Novel alkaline cellulases
ES2250969T3 (es) 1994-03-29 2006-04-16 Novozymes A/S Amilasa alcalina de bacilo.
WO1995030744A2 (en) 1994-05-04 1995-11-16 Genencor International Inc. Lipases with improved surfactant resistance
ATE222286T1 (de) 1994-06-17 2002-08-15 Genencor Int Reinigungsverfahren mit pflanzenzellwände abbauendes hemicellulase enzym enthaltender zusammensetzung und deren verwendung in reinigungsverfahren
DK0772684T3 (da) 1994-06-17 2005-12-12 Genencor Int Amylolytiske enzymer afledt fra B. Licheniformis alpha-amylasen med forbedrede karakteristika
AU2884595A (en) 1994-06-20 1996-01-15 Unilever Plc Modified pseudomonas lipases and their use
WO1996000292A1 (en) 1994-06-23 1996-01-04 Unilever N.V. Modified pseudomonas lipases and their use
CA2197203A1 (en) 1994-08-11 1996-02-22 Genencor International, Inc. An improved cleaning composition
ATE389012T1 (de) 1994-10-06 2008-03-15 Novozymes As Ein enzympräparat mit endoglucanase aktivität
BE1008998A3 (fr) 1994-10-14 1996-10-01 Solvay Lipase, microorganisme la produisant, procede de preparation de cette lipase et utilisations de celle-ci.
EP0785994A1 (de) 1994-10-26 1997-07-30 Novo Nordisk A/S Enzym mit lipolytischer aktivität
CN100419076C (zh) 1995-02-03 2008-09-17 诺沃奇梅兹有限公司 设计具有预定特性的α－淀粉酶突变体的方法
AR000862A1 (es) 1995-02-03 1997-08-06 Novozymes As Variantes de una ó-amilasa madre, un metodo para producir la misma, una estructura de adn y un vector de expresion, una celula transformada por dichaestructura de adn y vector, un aditivo para detergente, composicion detergente, una composicion para lavado de ropa y una composicion para la eliminacion del
JPH08228778A (ja) 1995-02-27 1996-09-10 Showa Denko Kk 新規なリパーゼ遺伝子及びそれを用いたリパーゼの製造方法
AU715423B2 (en) 1995-03-17 2000-02-03 Novozymes A/S Novel endoglucanases
AU718509B2 (en) 1995-03-24 2000-04-13 Genencor International, Inc. An improved laundry detergent composition comprising amylase
GB2303150A (en) 1995-07-08 1997-02-12 Procter & Gamble Laundry washing method
JP4307549B2 (ja) 1995-07-14 2009-08-05 ノボザイムス アクティーゼルスカブ 脂肪分解活性を有する修飾された酵素
ES2221934T3 (es) 1995-08-11 2005-01-16 Novozymes A/S Nuevas enzimas lipoliticas.
NZ319118A (en) 1995-09-13 2000-01-28 Genencor Int Thermophilic alkaliphilic bacteria derived from the genus Thermopallium
US5945394A (en) 1995-09-18 1999-08-31 Stepan Company Heavy duty liquid detergent compositions comprising salts of α-sulfonated fatty acid methyl esters and use of α-sulphonated fatty acid salts to inhibit redeposition of soil on fabric
ES2432519T3 (es) 1996-04-30 2013-12-04 Novozymes A/S Mutantes de alfa-amilasa
US6211134B1 (en) 1996-05-14 2001-04-03 Genecor International, Inc. Mutant α-amylase
US5763385A (en) 1996-05-14 1998-06-09 Genencor International, Inc. Modified α-amylases having altered calcium binding properties
DE19730542A1 (de) 1996-07-19 1998-02-12 Mibelle Ag Cosmetics Polymere Glucanäther-Derivate, ihre Herstellung sowie ihre Verwendung
WO1998008940A1 (en) 1996-08-26 1998-03-05 Novo Nordisk A/S A novel endoglucanase
EP0937138B1 (de) 1996-09-17 2006-04-26 Novozymes A/S Cellulasevarianten
WO1998015257A1 (en) 1996-10-08 1998-04-16 Novo Nordisk A/S Diaminobenzoic acid derivatives as dye precursors
WO1998026078A1 (en) 1996-12-09 1998-06-18 Genencor International, Inc. H mutant alpha-amylase enzymes
US6008026A (en) 1997-07-11 1999-12-28 Genencor International, Inc. Mutant α-amylase having introduced therein a disulfide bond
US6080568A (en) 1997-08-19 2000-06-27 Genencor International, Inc. Mutant α-amylase comprising modification at residues corresponding to A210, H405 and/or T412 in Bacillus licheniformis
GB9719637D0 (en) 1997-09-15 1997-11-19 Genencor Int Bv Proteases from gram-positive organisms
GB9719636D0 (en) 1997-09-15 1997-11-19 Genencor Int Bv Proteases from gram-positive organisms
JP4358431B2 (ja) 1997-10-13 2009-11-04 ノボザイムス アクティーゼルスカブ α−アミラーゼ変異体
MA25044A1 (fr) 1997-10-23 2000-10-01 Procter & Gamble Compositions de lavage contenant des variants de proteases multisubstituees.
CN1163597C (zh) 1997-10-30 2004-08-25 诺维信公司 α-淀粉酶突变体
US6562612B2 (en) 1997-11-19 2003-05-13 Genencor International, Inc. Cellulase producing actinomycetes, cellulase produced therefrom and method of producing same
GB9727471D0 (en) 1997-12-30 1998-02-25 Genencor Int Bv Proteases from gram positive organisms
GB9727464D0 (en) 1997-12-30 1998-02-25 Genencor Int Bv Proteases from gram positive organisms
US5952205A (en) 1998-02-06 1999-09-14 Neose Technologies, Inc. Process for processing sucrose into glucose and fructose
EP1054957A1 (de) 1998-02-18 2000-11-29 Novo Nordisk A/S Alkalische amylase von bacillus.
CN1292028B (zh) 1998-02-27 2013-08-14 诺维信公司 麦芽α淀粉酶变体
DK1066374T3 (da) 1998-02-27 2006-09-18 Novozymes As Amylolytiske enzymvarianter
AU2612499A (en) 1998-03-09 1999-09-27 Novo Nordisk A/S Enzymatic preparation of glucose syrup from starch
BRPI9911086B1 (pt) 1998-06-10 2016-08-02 Novozymes As composição de limpeza, processo para tratar tecidos a máquina, e uso de uma mananase
US6045780A (en) * 1998-06-22 2000-04-04 Shemberg Marketing Corporation Toothpaste composition
DE19834180A1 (de) 1998-07-29 2000-02-03 Benckiser Nv Zusammensetzung zur Verwendung in einer Geschirrspülmaschine
AU1200800A (en) 1998-10-13 2000-05-01 Procter & Gamble Company, The Detergent compositions or components
US6197565B1 (en) 1998-11-16 2001-03-06 Novo-Nordisk A/S α-Amylase variants
JP2000159806A (ja) * 1998-11-24 2000-06-13 Lion Corp カルボキシメチル化ムタン並びに化粧料
US7000000B1 (en) 1999-01-25 2006-02-14 E. I. Du Pont De Nemours And Company Polysaccharide fibers
KR19990068298A (ko) 1999-03-12 1999-09-06 정명우 장미씨기름을함유하는치약조성물
CA2365438C (en) 1999-03-30 2015-07-14 Novozymes A/S Alpha-amylase variants
CN100523181C (zh) 1999-03-31 2009-08-05 诺维信公司 具有碱性α-淀粉酶活性的多肽及其编码核酸
EP2889375B1 (de) 1999-03-31 2019-03-20 Novozymes A/S Polypeptide mit alkalischer Alpha-Amylase-Aktivität und Nukleinsäuren zur Codierung davon
CN1133654C (zh) 1999-08-05 2004-01-07 武汉大学 灵芝α-(1→3)-D-葡聚糖羧甲基化衍生物及其用途和制备方法
US6254645B1 (en) 1999-08-20 2001-07-03 Genencor International, Inc. Enzymatic modification of the surface of a polyester fiber or article
DE60033945T2 (de) 1999-08-20 2007-12-06 Novozymes A/S Alkalische amylase aus bacillus
US7012053B1 (en) 1999-10-22 2006-03-14 The Procter & Gamble Company Fabric care composition and method comprising a fabric care polysaccharide and wrinkle control agent
US6933140B1 (en) 1999-11-05 2005-08-23 Genencor International, Inc. Enzymes useful for changing the properties of polyester
EP1980614A3 (de) 1999-11-10 2009-04-08 Novozymes A/S Fungamyl-artige Alpha-Amylasevarianten
WO2001064852A1 (en) 2000-03-03 2001-09-07 Novozymes A/S Polypeptides having alkaline alpha-amylase activity and nucleic acids encoding same
EP2221365A1 (de) 2000-03-08 2010-08-25 Novozymes A/S Varianten mit veränderten Eigenschaften
US20030104969A1 (en) 2000-05-11 2003-06-05 Caswell Debra Sue Laundry system having unitized dosing
AU2001258229A1 (en) 2000-05-12 2001-11-26 Novozymes A/S Alpha-amylase variants with altered 1,6-activity
JP4230149B2 (ja) 2000-05-22 2009-02-25 明治製菓株式会社 エンドグルカナーゼ酵素ｎｃｅ５及びそれを含んでなるセルラーゼ調製物
AU2001273880A1 (en) 2000-06-14 2001-12-24 Novozymes A/S Pre-oxidized alpha-amylase
EP2204446A1 (de) 2000-08-01 2010-07-07 Novozymes A/S Alpha-Amylase-Mutanten mit veränderten Eigenschaften
US6440991B1 (en) 2000-10-02 2002-08-27 Wyeth Ethers of 7-desmethlrapamycin
EP1326965A2 (de) 2000-10-13 2003-07-16 Novozymes A/S Alpha-amylase-variante mit veränderten eigenschaften
EP1484389B1 (de) 2000-11-27 2006-05-10 The Procter & Gamble Company Reinigungsprodukte, Verfahren und Herstellung
PL362605A1 (en) 2000-11-27 2004-11-02 The Procter & Gamble Company Dishwashing method
SE520442C2 (sv) 2001-03-29 2003-07-08 Akzo Nobel Nv Användning av en kvartär ammoniumhydroxyethylcellulosaeter som balsam, kvartär ammoniumhydroxyethylcellulosaeter, process för tillverkning av cellulsaetern och komposition innehållande cellulosaetern
US7498158B2 (en) 2001-05-15 2009-03-03 Novozymes A/S Alpha-amylase variant with altered properties
NZ530638A (en) * 2001-07-20 2006-01-27 Tno Novel glucans and novel glucansucrases derived from lactic acid bacteria
US7056880B2 (en) 2002-02-28 2006-06-06 The Procter & Gamble Company Using cationic celluloses to enhance delivery of fabric care benefit agents
EP1354939A1 (de) 2002-04-19 2003-10-22 The Procter & Gamble Company Reinigungsmittelzusammensetzungen in Beuteln
JP4629664B2 (ja) 2003-04-29 2011-02-09 ジェネンコー・インターナショナル・インク 新規なバチルス０２９ｃｅｌセルラーゼ
EP1675941B1 (de) 2003-06-25 2013-05-22 Novozymes A/S Polypeptide mit alpha-amylase-aktivität und für diese codierende polynukleotide
US7306935B2 (en) 2003-06-25 2007-12-11 Novozymes North America, Inc Polypeptides having alpha-amylase activity and polypeptides encoding same
EP1648996B1 (de) 2003-06-25 2012-03-14 Novozymes A/S Enzyme zur stärkeverarbeitung
WO2005010093A1 (ja) 2003-07-09 2005-02-03 Ezaki Glico Co., Ltd. α－１，４－グルカンおよび／またはその修飾物を含む成型物およびその製造方法
WO2005018336A1 (en) 2003-08-22 2005-03-03 Novozymes A/S Process for preparing a dough comprising a starch-degrading glucogenic exo-amylase of family 13
CA2534710A1 (en) 2003-08-22 2005-03-03 Novozymes A/S Fungal alpha-amylase variants
ES2269907T3 (es) 2003-09-22 2007-04-01 THE PROCTER & GAMBLE COMPANY Composicion detergente en dosis unitaria liquida.
US7595182B2 (en) 2003-12-03 2009-09-29 Meiji Seika Kaisha, Ltd., Endoglucanase STCE and cellulase preparation containing the same
US7754460B2 (en) 2003-12-03 2010-07-13 Danisco Us Inc. Enzyme for the production of long chain peracid
EP2664670B1 (de) 2003-12-03 2015-05-06 Danisco US Inc. Perhydrolase
WO2005056783A1 (en) 2003-12-05 2005-06-23 Government Of The United States Of America As Represented By The Secretary Of The Department Of Health And Human Services Catalytic domains of beta(1,4)-galactosyltransferase i having altered metal ion specificity
DE10357260A1 (de) * 2003-12-08 2005-06-30 Degussa Food Ingredients Gmbh Polysaccharid-Derivate, deren Herstellung und Verwendung
CN1890367B (zh) 2003-12-08 2012-11-14 明治制果药业株式会社 耐表面活性剂的纤维素酶及其修饰方法
CA2552729C (en) 2004-01-08 2013-07-16 Novozymes A/S Amylase
DE102004020720A1 (de) 2004-04-28 2005-12-01 Henkel Kgaa Verfahren zur Herstellung von Wasch- oder Reinigungsmitteln
GB0416155D0 (en) 2004-07-20 2004-08-18 Unilever Plc Laundry product
US20080032024A1 (en) 2004-08-02 2008-02-07 Lars Beier Maltogenic Alpha-Amylase Variants
WO2006012902A2 (en) 2004-08-02 2006-02-09 Novozymes A/S Creation of diversity in polypeptides
US20060045854A1 (en) 2004-08-27 2006-03-02 Lynette Zaidel Oral care composition with cross-linked polymer peroxide
WO2006031554A2 (en) 2004-09-10 2006-03-23 Novozymes North America, Inc. Methods for preventing, removing, reducing, or disrupting biofilm
GB0423986D0 (en) 2004-10-29 2004-12-01 Unilever Plc Method of preparing a laundry product
US7659101B2 (en) 2004-12-15 2010-02-09 Novozymes A/S Alkaline Bacillus amylase
US20060134025A1 (en) 2004-12-17 2006-06-22 Colgate-Palmolive Company Oral compositions containing extracts of Rosmarinus and related methods
AR051863A1 (es) 2004-12-22 2007-02-14 Novozymes As Enzimas hibridas
AU2005318696B2 (en) 2004-12-23 2010-12-16 Novozymes A/S Alpha-amylase variants
DE602006013099D1 (de) 2005-02-17 2010-05-06 Procter & Gamble Zusammensetzung für die gewebepflege
US8017351B2 (en) 2005-06-24 2011-09-13 Novozymes A/S Amylases for pharmaceutical use
KR20080066921A (ko) 2005-10-12 2008-07-17 제넨코 인터내셔날 인코포레이티드 저장-안정성 중성 메탈로프로테아제의 용도 및 제조
US8076299B2 (en) 2005-10-25 2011-12-13 Riken Method for producing peptide thioester
GB2432852A (en) 2005-12-02 2007-06-06 Unilever Plc Laundry composition including polymer particles containing perfume and a cationic deposition aid
US20080057007A1 (en) 2006-03-01 2008-03-06 Dentech, Inc. Oral hygiene products containing ascorbic acid and method of using the same
CN101421383B (zh) 2006-03-02 2011-12-14 金克克国际有限公司 表面活性漂白和动态pH
EP1996692B2 (de) 2006-03-22 2020-04-01 The Procter and Gamble Company Flüssige behandlungszusammensetzung in einer einheitsdosis
JP4431992B2 (ja) * 2006-03-30 2010-03-17 高知県 保湿不織布
CA2655737A1 (en) 2006-06-30 2008-01-03 Novozymes A/S Bacterial alpha-amylase variants
GB0613069D0 (en) 2006-06-30 2006-08-09 Unilever Plc Laundry articles
KR20090031906A (ko) 2006-07-18 2009-03-30 다니스코 유에스 인크. 광범위한 온도에 걸쳐 활성인 프로테아제 변이형
US20080063617A1 (en) * 2006-09-07 2008-03-13 Abrahams John M Cosmetics formulations
EP2097519A2 (de) 2006-12-21 2009-09-09 Danisco US, INC., Genencor Division Zusammensetzungen und verwendung eines aplpha-amylase-polypeptids der bazillus-spezies 195
GB0700931D0 (en) 2007-01-18 2007-02-28 Reckitt Benckiser Nv Dosage element and a method of manufacturing a dosage element
CN101600794A (zh) 2007-02-01 2009-12-09 诺维信公司 α-淀粉酶及其用途
US8021863B2 (en) 2007-02-19 2011-09-20 Novozymes A/S Polypeptides with starch debranching activity
US20100151542A1 (en) 2007-02-27 2010-06-17 Mcauliffe Joseph C Cleaning Enzymes and Fragrance Production
MX2009008978A (es) 2007-02-27 2009-09-24 Danisco Us Inc Enzimas de limpieza y prevencion del mal olor.
US7576048B2 (en) 2007-04-04 2009-08-18 The Procter & Gamble Company Liquid laundry detergents containing cationic hydroxyethyl cellulose polymer
RU2010121930A (ru) 2007-10-31 2011-12-10 ДАНИСКО ЮЭс ИНК. (US) Применение и получение устойчивых к цитрату нейтральных металлопротеиназ
CA2704311C (en) 2007-11-01 2018-02-13 Danisco Us Inc. Production of thermolysin and variants thereof, and use in liquid detergents
MX2010004676A (es) 2007-11-05 2010-05-20 Danisco Us Inc Variantes de alfa-amilasa con propiedades alteradas.
WO2009098229A2 (en) 2008-02-04 2009-08-13 Danisco Us Inc., Genencor Division A method of preparing food products using ts23 alpha-amylase
ES2465228T5 (es) 2008-02-08 2022-03-18 Procter & Gamble Proceso para fabricar una bolsa soluble en agua
US8066818B2 (en) 2008-02-08 2011-11-29 The Procter & Gamble Company Water-soluble pouch
EP2098123A1 (de) 2008-03-07 2009-09-09 Bayer CropScience AG Verwendung von Alternan als Verdickungsmittel und Verdickungsmittelzusammensetzungen enthaltend Alternan und ein weiteres Verdickungsmittel.
US20090233830A1 (en) 2008-03-14 2009-09-17 Penny Sue Dirr Automatic detergent dishwashing composition
EP2100947A1 (de) 2008-03-14 2009-09-16 The Procter and Gamble Company Waschmittelzusammensetzung für Spülmaschinen
EP2107107A1 (de) 2008-04-02 2009-10-07 The Procter and Gamble Company Wasserlöslicher Beutel mit Waschmittelzusammensetzung
WO2009140504A1 (en) 2008-05-16 2009-11-19 Novozymes A/S Polypeptides having alpha-amylase activity and polynucleotides encoding same
WO2009149200A2 (en) 2008-06-06 2009-12-10 Danisco Us Inc. Compositions and methods comprising variant microbial proteases
ES2538406T3 (es) 2008-06-06 2015-06-19 Danisco Us Inc. Alfa-amilasas variantes de Bacillus subtilis y sus métodos de uso
PL2133410T3 (pl) 2008-06-13 2012-05-31 Procter & Gamble Saszetka wielokomorowa
JP5412522B2 (ja) 2008-11-11 2014-02-12 ダニスコ・ユーエス・インク スブチリシン変異体を含む組成物及び方法
AR074311A1 (es) 2008-11-11 2011-01-05 Danisco Us Inc Variantes de subtilisina aislada de bacillus, con actividad proteolitica
EP2647692A3 (de) 2008-11-11 2014-01-22 The Procter and Gamble Company Zusammensetzungen und Verfahren mit Serinproteasevarianten
ES2667812T3 (es) 2008-11-20 2018-05-14 Novozymes Inc. Polipéptidos que tienen actividad potenciadora amilolítica y polinucleótidos que codifican los mismos
US20100125046A1 (en) 2008-11-20 2010-05-20 Denome Frank William Cleaning products
EP2213717B1 (de) 2009-01-28 2017-06-28 The Procter & Gamble Company Zusammensetzung für einen Wäschebeutel mit mehreren Fächern
WO2010088447A1 (en) 2009-01-30 2010-08-05 Novozymes A/S Polypeptides having alpha-amylase activity and polynucleotides encoding same
EP3023483A1 (de) 2009-02-02 2016-05-25 The Procter and Gamble Company Flüssige handspülmittelzusammensetzung
WO2010091221A1 (en) 2009-02-06 2010-08-12 Novozymes A/S Polypeptides having alpha-amylase activity and polynucleotides encoding same
EP2216393B1 (de) 2009-02-09 2024-04-24 The Procter & Gamble Company Reinigungsmittelzusammensetzung
EP2406373B1 (de) 2009-03-10 2014-05-28 Danisco US Inc. Alpha-amylase aus bacillus megaterium dsm90, verwandte amylasen und deren verwendung
CA2757343A1 (en) 2009-04-01 2010-10-07 Danisco Us Inc. Compositions and methods comprising alpha-amylase variants with altered properties
WO2010117511A1 (en) 2009-04-08 2010-10-14 Danisco Us Inc. Halomonas strain wdg195-related alpha-amylases, and methods of use, thereof
GB0906281D0 (en) 2009-04-09 2009-05-20 Reckitt Benckiser Nv Detergent compositions
PL2508436T3 (pl) 2009-05-19 2018-01-31 Procter & Gamble Sposób drukowania na powłoce rozpuszczalnej w wodzie
GB0916485D0 (en) 2009-09-18 2009-10-28 Hammond Peter Improved materials
BR112012014082B1 (pt) 2009-12-09 2020-12-15 Danisco Us Inc variante de protease isolada e seu método de produção, ácido nucleico isolado, vetor de expressão, célula hospedeira recombinante, composição e método para limpeza de um item ou de uma superfície em necessidade de limpeza
EP2516640A2 (de) 2009-12-22 2012-10-31 Novozymes A/S Pullulanasevarianten und ihre verwendung
WO2011076897A1 (en) 2009-12-22 2011-06-30 Novozymes A/S Use of amylase variants at low temperature
MX349630B (es) 2010-01-04 2017-08-07 Novozymes As Alfa-amilasas.
US8905236B2 (en) 2010-01-29 2014-12-09 Monosol, Llc Water-soluble film having improved dissolution and stress properties, and packets made therefrom
EP3892709A3 (de) 2010-02-10 2022-01-19 Novozymes A/S Varianten und zusammensetzungen mit varianten mit hoher stabilität in gegenwart eines chelatwirkstoffs
US20110240510A1 (en) 2010-04-06 2011-10-06 Johan Maurice Theo De Poortere Optimized release of bleaching systems in laundry detergents
BR112012028467B1 (pt) 2010-05-06 2021-02-17 Danisco Us Inc. variantes de subtilisina, seu método de produção, ácido nucleico, e método de limpeza
PL2399979T5 (pl) 2010-06-24 2022-05-30 The Procter And Gamble Company Rozpuszczalne produkty w dawkach jednostkowych zwierające polimer kationowy
PL2609183T3 (pl) 2010-08-23 2019-05-31 Henkel IP & Holding GmbH Kompozycje detergentowe w dawkach jednostkowych i sposoby ich wytwarzania i zastosowania
WO2012059336A1 (en) 2010-11-03 2012-05-10 Henkel Ag & Co. Kgaa Laundry article having cleaning properties
GB201101536D0 (en) 2011-01-31 2011-03-16 Reckitt Benckiser Nv Cleaning article
JP5896799B2 (ja) 2011-03-28 2016-03-30 株式会社Adeka カチオン化βグルカン
BR112013027963A2 (pt) 2011-05-05 2016-11-29 Danisco Us Inc "variante de subtilisina com atividade proteolítica, ácido nucleico, vetor de expressão, célula hospedeira, composição e método de limpeza".
IN2014MN00272A (de) 2011-08-24 2015-06-19 Unilever Plc
MX2014002079A (es) 2011-08-24 2014-05-30 Unilever Nv Particulas de liberacion de un agente benefico que comprende dextrano.
US8642757B2 (en) 2011-09-09 2014-02-04 E I Du Pont De Nemours And Company High titer production of highly linear poly (α 1,3 glucan)
US9080195B2 (en) * 2011-09-09 2015-07-14 E I Du Pont De Nemours And Company High titer production of poly (α 1,3 glucan)
GB201119367D0 (en) 2011-11-10 2011-12-21 M I Drilling Fluids Uk Ltd Composition and method
US8828689B2 (en) * 2011-12-19 2014-09-09 E I Du Pont De Nemours And Company Increased poly (α 1, 3 glucan) yield using boric acid
US9150734B2 (en) 2012-03-07 2015-10-06 Empire Technology Development Llc Zwitterionic lignin derivatives for marine antifouling coatings
JP2015519312A (ja) 2012-04-19 2015-07-09 パーデュー・リサーチ・ファウンデーションＰｕｒｄｕｅ Ｒｅｓｅａｒｃｈ Ｆｏｕｎｄａｔｉｏｎ 高度分岐α−Ｄ−グルカン
WO2014052386A2 (en) 2012-09-25 2014-04-03 E. I. Du Pont De Nemours And Company Glucosyltransferase enzymes for production of glucan polymers
NZ708491A (en) * 2012-12-20 2019-10-25 Du Pont Preparation of poly alpha-1,3-glucan ethers
US9139718B2 (en) 2012-12-20 2015-09-22 E I Du Pont De Nemours And Company Preparation of poly alpha-1,3-glucan ethers
EP3083704B1 (de) 2013-12-16 2022-08-17 Nutrition & Biosciences USA 4, Inc. Verwendung von poly-alpha-1,3-glucan-ethern als viskositätsmodifikatoren
BR112016014014B1 (pt) * 2013-12-18 2021-08-10 Nutrition & Biosciences USA 4, Inc. Composição, método para a produção de um composto e método para o tratamento de um material
US20150232785A1 (en) 2014-02-14 2015-08-20 E I Du Pont De Nemours And Company Polysaccharides for viscosity modification
US9714403B2 (en) 2014-06-19 2017-07-25 E I Du Pont De Nemours And Company Compositions containing one or more poly alpha-1,3-glucan ether compounds
WO2015195777A1 (en) 2014-06-19 2015-12-23 E. I. Du Pont De Nemours And Company Compositions containing one or more poly alpha-1,3-glucan ether compounds
JP6956013B2 (ja) * 2015-06-01 2021-10-27 ニュートリション・アンド・バイオサイエンシーズ・ユーエスエー・フォー，インコーポレイテッド ポリα−１，３−グルカンフィブリッド及びその使用、並びにポリα−１，３−グルカンフィブリッドを製造する方法
WO2017083226A1 (en) * 2015-11-13 2017-05-18 E. I. Du Pont De Nemours And Company Glucan fiber compositions for use in laundry care and fabric care
WO2018119518A1 (en) * 2017-01-01 2018-07-05 Lee Chi Yu Gregory Rp215 chimeric antigen receptor construct and methods of making and using same
KR20190135492A (ko) * 2017-04-25 2019-12-06 이 아이 듀폰 디 네모아 앤드 캄파니 산소 차단성을 갖는 다당류 코팅
JP2021507955A (ja) * 2017-12-14 2021-02-25 デュポン・インダストリアル・バイオサイエンシーズ・ユーエスエイ・エルエルシー α−１，３−グルカングラフトコポリマー
US20210253977A1 (en) * 2018-06-20 2021-08-19 Dupont Industrial Biosciences Usa, Llc Polysaccharide derivatives and compositions comprising same
CA3207822A1 (en) * 2018-06-20 2019-12-26 The Procter & Gamble Company A fabric care or home care product comprising polysaccharide derivatives

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CA2932498C (en) 2023-03-14
US20220306770A1 (en) 2022-09-29
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EP4163305A1 (de) 2023-04-12
KR20160099629A (ko) 2016-08-22
US10005850B2 (en) 2018-06-26
AU2014366222A1 (en) 2016-06-09
WO2015095046A1 (en) 2015-06-25
JP6598778B2 (ja) 2019-10-30
CN106255707B (zh) 2019-06-18
US20160304629A1 (en) 2016-10-20
CN106255707A (zh) 2016-12-21
BR112016013684A2 (pt) 2017-08-08
EP3083704A1 (de) 2016-10-26
US10865254B2 (en) 2020-12-15
US20180291122A1 (en) 2018-10-11
US20210261692A1 (en) 2021-08-26
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AU2014366222B2 (en) 2018-07-19

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